Composition for dyeing keratin fibres comprising a direct dye bearing a disulphide/thiol function, a nonionic surfactant, an amphoteric surfactant, an ethoxylated fatty alcohol, an alkaline agent and a reducing agent

ABSTRACT

The invention relates to a process for dyeing and/or lightening keratin fibres such as the hair, using i) at least one direct dye bearing a disulfide, thiol or protected-thiol function and ii) at least one nonionic surfactant, iii) at least one amphoteric surfactant, iv) at least one alkaline agent, and v) at least one reducing agent. The invention also relates to a composition comprising the ingredients i) to v), to the use of the combination of i), ii), iii), iv) and v) for the dyeing and/or lightening of keratin fibres, and to a multi-compartment kit comprising the ingredients i) to v). The dyeing process and the composition according to the invention especially afford a long-lasting coloration on keratin fibres, which is strong, chromatic and/or homogeneous, with or without the use of an oxidizing agent.

CROSS REFERENCE TO RELATED APPLICATIONS

This is a national stage application of PCT/EP2012/052748, filedinternationally on Feb. 17, 2012, which claims priority to U.S.Provisional Application No. 61/448,769, filed on Mar. 3, 2011, as wellas French Application No. FR 1151555, filed on Feb. 25, 2011, all ofwhich are incorporated herein by reference in their entireties.

The invention relates to a process for dyeing and/or lightening keratinfibres using direct dyes.

It is known practice to dye keratin fibres by direct dyeing orsemi-permanent dyeing. Direct dyeing or semi-permanent dyeing consistsin introducing colour via a coloured molecule that becomes adsorbed ontothe surface of the hair or that penetrates into the hair. Thus, theprocess conventionally used in direct dyeing consists in applying tokeratin fibres direct dyes, which are coloured and colouring moleculesthat have affinity for the fibres, leaving the fibres in contact withthe colouring molecules and then optionally rinsing the fibres.Generally, this technique leads to chromatic colorations.

Scientific research has been conducted for several years to modify thecolour of keratin materials, especially keratin fibres, and inparticular to mask white fibres, to modify the colour of the fibrespermanently or temporarily, and to satisfy new desires and needs interms of colours and durability.

Patent applications EP 1 647 580, WO 2005/097 051, EP 2 004 759, EP 2075 289, WO 2007/110 541, WO 2007/110 540, WO 2007/110 539, WO 2007/110538, WO 2007/110 537, WO 2007/110 536, WO 2007/110 535, WO 2007/110 534,WO 2007/110 533, WO 2007/110 532, WO 2007/110 531, EP 2 070 988, WO2009/040 354 and WO 2009/034 059 disclose direct dyes bearing adisulfide, thiol or protected-thiol function, for dyeing the hair. Thecolours obtained are not sufficiently satisfactory, especially in termsof coloration intensity, colour selectivity between the root and theend, and chromaticity of the colour.

The aim of the present invention is to provide novel systems for dyeingthe hair, which make it possible, even without the use of a chemicaloxidizing agent, to obtain improved colorations, especially in terms offastness with respect to external agents, homogeneity of the coloration(little selectivity between the root and the end of the keratin fibres),and intensity, and/or which do not impair the cosmetic properties of thekeratin fibres.

This aim is achieved with the present invention, a first subject ofwhich is a cosmetic composition comprising:

-   i) at least one direct dye bearing a disulfide function, a thiol    function or a protected-thiol function, especially of formula (I):    A-(X)p-Csat-S—U  (I)    -    salts thereof with an organic or mineral acid, optical or        geometric isomers thereof, tautomers thereof, and solvates        thereof such as the hydrates,    -   in which formula (I):        -   U represents a radical chosen from:            -   a) —S—C′_(sat)—(X′)p′-A′; and            -   b) —Y;        -   A and A′, which may be identical or different, represent a            radical containing at least one quaternized cationic            chromophore or at least one chromophore bearing a            quaternized or quaternizable group;        -   Y represents i) a hydrogen atom; or ii) a thiol-function            protecting group;        -   X and X′, which may be identical or different, represent a            linear or branched, saturated or unsaturated divalent C1-C30            hydrocarbon-based chain, optionally interrupted and/or            optionally terminated at one or both of its ends with one or            more divalent groups or combinations thereof chosen from:            -   —N(R)—, —N+(R)(R)—, —O—, —S—, —CO—, —SO2- with R, which                may be identical or different, chosen from a hydrogen                and a C1-C4 alkyl, hydroxyalkyl or aminoalkyl radical;            -   an aromatic or non-aromatic, saturated or unsaturated,                fused or non-fused (hetero)cyclic radical optionally                comprising one or more identical or different,                optionally substituted heteroatoms;        -   p and p′, which may be identical or different, are equal to            0 or 1;        -   C_(sat) and C′_(sat), which may be identical or different,            represent an optionally substituted linear or branched, or            cyclic, C1-C18 alkylene chain;-   ii) at least one nonionic surfactant;-   iii) at least one amphoteric surfactant;-   iv) at least one alkaline agent; and-   v) at least one reducing agent.

Another subject of the invention is a process for dyeing and/orlightening keratin fibres, especially dark keratin fibres, by applyingto the said fibres the ingredients i) to iv) as defined previously, thesaid ingredients being applied together or separately.

Another subject of the invention is the use of the compositioncomprising i), ii), iii), iv) and v) as defined previously, for thedyeing and/or lightening of keratin fibres.

Another subject of the invention is a multi-compartment kit comprisingi), ii), iii), iv) and v) as defined previously.

The colorations obtained are attractive, aesthetic, intense, strong,chromatic and very fast or persistent with respect to common attackingfactors or everyday assaults such as sun, sebum and especially withrespect to perspiration, and other hair treatments such as successiveshampooing, while at the same time respecting the keratin fibres. Theintensity obtained is particularly noteworthy. The same is true for thecolour homogeneity or selectivity of the colour.

For the purposes of the present invention, and unless otherwiseindicated:

-   -   a “direct dye bearing a disulfide function” is a direct dye        comprising one or more cationic chromophores that absorb light        in the visible spectrum, and comprising a disulfide bond: —S—S—        between two carbon atoms and is preferably indirectly bonded to        the chromophore(s) of the dye, i.e. between the chromophores and        the —S—S— function there is at least one methylene group;    -   a “direct dye bearing a protected-thiol function” is a direct        dye comprising a chromophore, comprising a protected-thiol        function —SY in which Y is a protecting group known to those        skilled in the art, for instance those described in the        publications Protective Groups in Organic Synthesis, T. W.        Greene, John Wiley & Sons ed., NY, 1981, pp. 193-217; Protecting        Groups, P. Kocienski, Thieme, 3^(rd) ed., 2005, chap. 5; and        Ullmann's Encyclopedia, Peptide Synthesis, pp. 4-5, 2005        Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim 10.1002/14356007.a19        157; it being understood that the said protected-thiol function        is preferably indirectly bonded to the chromophore of the dye,        i.e. between the chromophore and the function —SY there is at        least one methylene group;    -   a “direct dye bearing a thiol function” is a direct dye        comprising a chromophore, and comprising a thiol function —SY′        in which Y′ is i) a hydrogen atom; ii) an alkali metal; iii) an        alkaline-earth metal; iv) an ammonium group:        N⁺R^(α)R^(β)R^(γ)R^(δ) or a phosphonium group:        P⁺R^(α)R^(β)R^(γ)R^(δ) with R^(α), R^(β), R^(γ) and R^(δ), which        may be identical or different, representing a hydrogen atom or a        group (C₁-C₄)alkyl, preferentially comprising a thiol function        —SH, it being understood that the said thiol function is        preferably indirectly bonded to the chromophore of the dye, i.e.        between the chromophore and the function —SY′ there is at least        one methylene group;    -   a “chromophore” is a radical derived from a dye, i.e. a radical        derived from a molecule that absorbs light in the visible        radiation range that is visually perceptible by man, i.e. an        absorption wavelength λ_(abs) inclusively between 400 and 800        nm; the chromophore may be fluorescent, i.e. it is capable of        absorbing in the UV and visible radiation range at a wavelength        λ_(abs) between 250 and 800 nm and capable of re-emitting in the        visible range at an emission wavelength λ_(em) between 400 and        800 nm;    -   a “chromophore” is said to be “quaternized cationic” or “bearing        a quaternized cationic group” if it comprises in its structure        at least one permanent cationic charge formed from at least one        quaternized nitrogen atom (ammonium) or quaternized phosphorus        atom (phosphonium), preferably nitrogen;    -   a group is said to be “bearing a quaternizable cationic group”        when it comprises in its structure at least one tertiary amine        or one tertiary phosphine at the end of a hydrocarbon-based        chain, preferably C₁-C₁₀ alkyl, and in particular such as        —(CR′R″)_(p)—N(R_(a))—R_(b) with R′ and R″, which may be        identical or different, representing a hydrogen atom or a        (C₁-C₆)alkyl group; R_(a) and R_(b), which may be identical or        different, representing a (C₁-C₆)alkyl group, a        monohydroxy(C₁-C₆)alkyl group, a (poly)(hydroxy)(C₁-C₆)alkyl        group or R_(a) and R_(b) form, together with the nitrogen atom        that bears them, a heterocycloalkyl group such as morpholino,        which, once quaternized, will become morpholinium, piperidino,        which, once quaternized, will become piperidinium, imidazolyl,        which, once quaternized, will become imidazolium or piperazino,        which, once quaternized, will become piperazinium; and p        representing an integer between 1 and 10 inclusive; preferably,        R′ and R″ represent a hydrogen atom, R_(a) and R_(b) represent a        (C₁-C₄)alkyl group and p is between 2 and 5;    -   the dyes according to the invention contain one or more        chromophores, and these dyes are capable of absorbing light at a        wavelength λ_(abs) particularly of between 400 and 700 nm        inclusive;    -   the “fluorescent” dyes according to the invention are dyes        containing at least one fluorescent chromophore, and these dyes        are capable of absorbing in the visible range at a wavelength        λ_(abs) particularly between 400 and 800 nm and of re-emitting        in the visible range at a longer wavelength λ_(em) than that        absorbed, of between 400 and 800 nm. The difference between the        absorption and emission wavelengths, also known as the Stoke's        shift, is between 1 nm and 100 nm. More preferentially,        fluorescent dyes are dyes that are capable of absorbing at a        wavelength λ_(abs) of between 420 nm and 550 nm and of        re-emitting in the visible range at a wavelength λ_(em) between        470 and 600 nm;    -   chromophores are said to be “different” when they differ in        their chemical structure and may be chromophores derived from        different families or from the same family on condition that        they have different chemical structures: for example, the        chromophores may be chosen from the family of azo dyes but        differ in the chemical structure of the radicals constituting        them or in the respective position of these radicals;    -   an “alkylene chain” represents a divalent acyclic C₁-C₂₀        hydrocarbon-based chain; particularly C₁-C₆ and more        particularly C₁-C₂ when the chain is linear; optionally        substituted with one or more groups, which may be identical or        different, chosen from i) hydroxyl, ii) (C₁-C₂)alkoxy, iii)        (poly)hydroxy(C₂-C₄)alkoxy(di)(C₁-C₂)(alkyl)amino, iv)        R^(a)—Z^(a)—C(Z^(b))—Z^(c)—, and v) R^(a)—Z^(a)—S(O)_(t)—Z^(c)—        with Z^(a) and Z^(b), which may be identical or different,        representing an oxygen or sulfur atom, or a group NR^(a)′,        Z^(c), representing a bond, an oxygen or sulfur atom, or a group        NR^(a); R^(a), representing an alkali metal, a hydrogen atom, an        alkyl group, or alternatively is absent if another part of the        cationic molecule and R^(a)′ representing a hydrogen atom or an        alkyl group and t is equal to 1 or 2; more particularly, the        groups iv) are chosen from carboxylate —C(O)O⁻ or —C(O)OMetal        (metal=alkali metal), carboxyl —C(O)—OH, guanidino        H₂H—C(NH₂)—NH—, amidino H₂H—C(NH₂)—, (thio)ureo H₂N—C(O)—NH— and        H₂N—C(S)—NH—, aminocarbonyl —C(O)—NRa′₂ or aminothiocarbonyl        —C(S)—NRa′₂; carbamoyl Ra′—C(O)—NRa′— or thiocarbamoyl        Ra′—C(S)—NRa′— with Ra′, which may be identical or different,        representing a hydrogen atom or a (C₁-C₄)alkyl group;    -   an “optionally substituted, saturated or unsaturated C₁-C₃₀        divalent hydrocarbon-based chain” represents a hydrocarbon-based        chain, particularly of C₁-C₈, optionally comprising one or more        conjugated or unconjugated π double bonds, and in particular the        hydrocarbon-based chain is saturated; the said chain is        optionally substituted with one or more groups, which may be        identical or different, chosen from i) hydroxyl, ii)        (C₁-C₂)alkoxy, iii)        (poly)hydroxy(C₂-C₄)alkoxy(di)(C₁-C₂)(alkyl)amino, iv)        R^(a)—Z^(a)—C(Z^(b))—Z^(c)—, and v) R^(a)—Z^(a)—S(O)_(t)—Z^(c)—        with Z^(a) and Z^(b), which may be identical or different,        representing an oxygen or sulfur atom, or a group NR^(a)′,        Z^(c), representing a bond, an oxygen or sulfur atom, or a group        NR^(a); R^(a), representing an alkali metal, a hydrogen atom, an        alkyl group, or alternatively is absent if another part of the        cationic molecule and R^(a)′ representing a hydrogen atom or an        alkyl group and t is equal to 1 or 2; more particularly, the        groups iv) are chosen from carboxylate —C(O)O⁻ or —C(O)OMetal        (metal=alkali metal), carboxyl —C(O)—OH, guanidino        H₂H—C(NH₂)—NH—, amidino H₂H—C(NH₂)—, (thio)ureo H₂N—C(O)—NH— and        H₂N—C(S)—NH—, aminocarbonyl —C(O)—NRa′₂ or aminothiocarbonyl        —C(S)—NRa′₂; carbamoyl Ra′—C(O)—NRa′— or thiocarbamoyl        Ra′—C(S)—NRa′— with Ra′, which may be identical or different,        representing a hydrogen atom or a (C₁-C₄)alkyl group;    -   the “aryl” or “heteroaryl” radicals or the aryl or heteroaryl        part of a radical may be substituted with at least one        substituent borne by a carbon atom, chosen from:        -   a C1-C16 and preferably C1-C8 alkyl radical optionally            substituted with one or more radicals chosen from hydroxyl,            C1-C2 alkoxy, C2-C4 (poly)hydroxyalkoxy, acylamino, amino            substituted with two C1-C4 alkyl radicals, which may be            identical or different, optionally bearing at least one            hydroxyl group, or the two radicals possibly forming, with            the nitrogen atom to which they are attached, a saturated or            unsaturated, optionally substituted 5- to 7-membered and            preferably 5- or 6-membered heterocycle optionally            comprising another nitrogen or non-nitrogen heteroatom;        -   a halogen atom;        -   a hydroxyl group;        -   a C₁-C₂ alkoxy radical;        -   a C₂-C₄ (poly)hydroxyalkoxy radical;        -   an amino radical;        -   a 5- or 6-membered heterocycloalkyl radical;        -   an optionally cationic 5- or 6-membered heteroaryl radical,            preferentially imidazolium, optionally substituted with a            (C₁-C₄)alkyl radical, preferentially methyl;        -   an amino radical substituted with one or two identical or            different C₁-C₆ alkyl radicals, optionally bearing at least:            -   i) a hydroxyl group,            -   ii) an amino group optionally substituted with one or                two optionally substituted C₁-C₃ alkyl radicals, the                said alkyl radicals possibly forming with the nitrogen                atom to which they are attached a saturated or                unsaturated, optionally substituted 5- to 7-membered                heterocycle, optionally comprising at least one other                nitrogen or non-nitrogen heteroatom,            -   iii) a quaternary ammonium group —N+R′R″R′″, M- for                which R′, R″ and R′″, which may be identical or                different, represent a hydrogen atom or a C₁-C₄ alkyl                group; and M- represents the counterion of the organic                or mineral acid or of the corresponding halide; or            -   iv) an optionally cationic 5- or 6-membered heteroaryl                radical, preferentially imidazolium, optionally                substituted with a (C₁-C₄)alkyl radical, preferentially                methyl;        -   an acylamino radical (—NR—C(O)—R′) in which the radical R is            a hydrogen atom or a C₁-C₄ alkyl radical optionally bearing            at least one hydroxyl group and the radical R′ is a C₁-C₂            alkyl radical;        -   a carbamoyl radical ((R)₂N—C(O)—) in which the radicals R,            which may be identical or different, represent a hydrogen            atom or a C₁-C₄ alkyl radical optionally bearing at least            one hydroxyl group;        -   an alkylsulfonylamino radical (R′—S(O)₂—N(R)—) in which the            radical R represents a hydrogen atom or a C₁-C₄ alkyl            radical optionally bearing at least one hydroxyl group and            the radical R′ represents a C₁-C₄ alkyl radical, or a phenyl            radical;        -   an aminosulfonyl radical ((R)₂N—S(O)₂—) in which the            radicals R, which may be identical or different, represent a            hydrogen atom or a C₁-C₄ alkyl radical optionally bearing at            least one hydroxyl group;        -   a carboxylic radical in acid or salified form (preferably            with an alkali metal or a substituted or unsubstituted            ammonium);        -   a cyano group;        -   a nitro or nitroso group;        -   a polyhaloalkyl group, preferentially trifluoromethyl;    -   the cyclic or heterocyclic part of a non-aromatic radical may be        substituted with at least one substituent chosen from the        following groups:        -   hydroxyl;        -   C₁-C₄ alkoxy, C₂-C₄ (poly)hydroxyalkoxy,        -   (C₁-C₄)alkyl;        -   alkylcarbonylamino (R—C(O)—NR′—) in which the radical R′ is            a hydrogen atom or a C₁-C₄ alkyl radical optionally bearing            at least one hydroxyl group, and the radical R is a C₁-C₂            alkyl radical or an amino optionally substituted with one or            two C₁-C₄ alkyl groups, which may be identical or different,            themselves optionally bearing at least one hydroxyl group,            the said alkyl radicals possibly forming, with the nitrogen            atom to which they are attached, a saturated or unsaturated,            optionally substituted 5- to 7-membered heterocycle,            optionally comprising at least one other nitrogen or            non-nitrogen heteroatom;        -   alkylcarbonyloxy (R—C(O)—O—) in which the radical R is a            C₁-C₄ alkyl radical or an amino group optionally substituted            with one or two identical or different C₁-C₄ alkyl groups,            themselves optionally bearing at least one hydroxyl group,            the said alkyl radicals possibly forming with the nitrogen            atom to which they are attached a saturated or unsaturated,            optionally substituted 5- to 7-membered heterocycle,            optionally comprising at least one other nitrogen or            non-nitrogen heteroatom;        -   alkoxycarbonyl (R-G-C(O)—) in which the radical R is a C₁-C₄            alkoxy radical, G is an oxygen atom or an amino group            optionally substituted with a C₁-C₄ alkyl group itself            optionally bearing at least one hydroxyl group, the said            alkyl radical possibly forming, with the nitrogen atom to            which they are attached, a saturated or unsaturated,            optionally substituted 5- to 7-membered heterocycle,            optionally comprising at least one other nitrogen or            non-nitrogen heteroatom;    -   a cyclic or heterocyclic radical, or a non-aromatic portion of        an aryl or heteroaryl radical, may also be substituted with one        or more oxo groups;    -   a hydrocarbon-based chain is unsaturated when it comprises one        or more double bonds and/or one or more triple bonds;    -   an “aryl” radical represents a fused or non-fused monocyclic or        polycyclic carbon-based group containing from 6 to 22 carbon        atoms, and in which at least one ring is aromatic;        preferentially, the aryl radical is a phenyl, biphenyl,        naphthyl, indenyl, anthracenyl or tetrahydronaphthyl;    -   a “heteroaryl radical” represents a fused or non-fused,        optionally cationic, 5- to 22-membered monocyclic or polycyclic        group, comprising from 1 to 6 heteroatoms chosen from nitrogen,        oxygen, sulfur and selenium, and at least one ring of which is        aromatic; preferentially, a heteroaryl radical is chosen from        acridinyl, benzimidazolyl, benzobistriazolyl, benzopyrazolyl,        benzopyridazinyl, benzoquinolyl, benzothiazolyl, benzotriazolyl,        benzoxazolyl, pyridyl, tetrazolyl, dihydrothiazolyl,        imidazopyridyl, imidazolyl, indolyl, isoquinolyl,        naphthoimidazolyl, naphthoxazolyl, naphthopyrazolyl,        oxadiazolyl, oxazolyl, oxazolopyridyl, phenazinyl, phenoxazolyl,        pyrazinyl, pyrazolyl, pyrilyl, pyrazoyltriazyl, pyridyl,        pyridinoimidazolyl, pyrrolyl, quinolyl, tetrazolyl,        thiadiazolyl, thiazolyl, thiazolopyridyl, thiazoylimidazolyl,        thiopyrylyl, triazolyl, xanthyl and the ammonium salt thereof;    -   a “heterocyclic radical” is a fused or non-fused, 5- to        22-membered monocyclic or polycyclic radical, comprising from 1        to 6 heteroatoms chosen from nitrogen, oxygen, sulfur and        selenium, which may contain one or two unsaturations, but is        non-aromatic;    -   a “heterocycloalkyl radical” is a heterocyclic radical        comprising at least one saturated ring;    -   a “cationic heteroaryl radical” is a heteroaryl group as defined        previously, which comprises a quaternized endocyclic or        exocyclic cationic group,        -   when the cationic charge is endocyclic, it is included in            the electron delocalization via the mesomeric effect, for            example it is a pyridinium, imidazolium or indolinium group;

-   -   -    with R and R′ being a heteroaryl substituent as defined            previously and particularly a (hydroxy)(C₁-C₈)alkyl group            such as methyl;        -   when the cationic charge is exocyclic, for example, it is an            ammonium or phosphonium substituent R⁺ such as            trimethylammonium, which is outside the heteroaryl such as            pyridyl, indolyl, imidazolyl or naphthalimidyl in question;

-   -   -    with R being a heteroaryl substituent as defined previously            and R⁺ an ammonium R_(a)R_(b)R_(c)N⁺—, phosphonium            R_(a)R_(b)R_(c)P⁺— or ammonium            R_(a)R_(b)R_(c)N⁺—(C₁-C₆)alkylamino group with R_(a), R_(b)            and R_(c), which may be identical or different, representing            a hydrogen atom or a (C₁-C₈)alkyl group such as methyl;

    -   the term “cationic aryl bearing an exocyclic charge” means an        aryl ring whose quaternized cationic group is outside the said        ring: it is especially an ammonium or phosphonium substituent R⁺        such as trimethylammonium, which is outside the aryl such as        phenyl or naphthyl:

-   -   an “alkyl radical” is a linear or branched C₁-C₂₀ and preferably        C₁-C₈ hydrocarbon-based radical;    -   an “alkenylene radical” is an unsaturated hydrocarbon-based        divalent radical as defined previously, which may contain from 1        to 4 conjugated or unconjugated double bonds —C═C—; the        alkenylene group particularly contains 1 or 2 unsaturations;    -   the term “optionally substituted” attributed to the alkyl        radical means that the said alkyl radical may be substituted        with one or more radicals chosen from the following radicals: i)        hydroxyl, ii) C₁-C₄ alkoxy, iii) acylamino, iv) amino optionally        substituted with one or two identical or different C₁-C₄ alkyl        radicals, the said alkyl radicals possibly forming with the        nitrogen atom that bears them a 5- to 7-membered heterocycle,        optionally comprising another nitrogen or non-nitrogen        heteroatom; v) or a quaternary ammonium group —N⁺R′R″R′″, M⁻ for        which R′, R″ and R′″, which may be identical or different,        represent a hydrogen atom or a C₁-C₄ alkyl group, or else        —N⁺R′R″R′″, forms a heteroaryl such as imidazolium optionally        substituted with a C₁-C₄ alkyl group, and M⁻ represents the        counterion of the organic or mineral acid or of the        corresponding halide;    -   an “alkoxy radical” is an alkyl-oxy radical for which the alkyl        radical is a linear or branched C₁-C₁₆ and preferentially C₁-C₈        hydrocarbon-based radical;    -   when the alkoxy group is optionally substituted, this implies        that the alkyl group is optionally substituted as defined        hereinabove;    -   the “tone depth” is the unit known to hairstyling professionals,        published in the book Sciences des traitements capillaires [Hair        treatment sciences] by Charles Zviak, 1988, published by Masson,        pp. 215 and 278; the tone depths range from 1 (black) to 10        (very light blond), one unit corresponding to one tone; the        higher the figure, the lighter the shade;    -   a “dark” keratin fibre is a keratin fibre whose lightness L*        measured in the CIE L*a*b* system is less than or equal to 45        and preferably less than or equal to 40, given that L*=0 is        equivalent to black and L*=100 is equivalent to white;    -   “naturally or artificially dark hair” means hair whose tone        depth is less than or equal to 6 (dark blond) and preferably        less than or equal to 4 (chestnut-brown). Artificially dyed hair        is hair whose colour has been modified by a coloration        treatment, for example a coloration with direct dyes or        oxidation dyes;    -   an “organic or mineral acid salt” is more particularly chosen        from salts chosen from a salt derived from i) hydrochloric acid        HCl, ii) hydrobromic acid HBr, iii) sulfuric acid H₂SO₄, iv)        alkylsulfonic acids: Alk-S(O)₂OH such as methanesulfonic acid        and ethanesulfonic acid; v) arylsulfonic acids: Ar—S(O)₂OH such        as benzenesulfonic acid and toluenesulfonic acid; vi) citric        acid; vii) succinic acid; viii) tartaric acid; ix) lactic        acid; x) alkoxysulfinic acids: Alk-O—S(O)OH such as        methoxysulfinic acid and ethoxysulfinic acid; xi)        aryloxysulfinic acids such as tolueneoxysulfinic acid and        phenoxysulfinic acid; xii) phosphoric acid H₃PO₄; xiii) acetic        acid CH₃C(O)OH; xiv) triflic acid CF₃SO₃H; and xv)        tetrafluoroboric acid HBF₄;    -   an “anionic counterion” means an anion or an anionic group        derived from an organic or mineral acid which counterbalances        the cationic charge of the dye; more particularly, the anionic        counterion is chosen from i) halides such as chloride or        bromide; ii) nitrates; iii) sulfonates, including C₁-C₆        alkylsulfonates: Alk-S(O)₂O⁻ such as methanesulfonate or        mesylate and ethanesulfonate; iv) arylsulfonates: Ar—S(O)₂O⁻        such as benzenesulfonate and toluenesulfonate or tosylate; v)        citrate; vi) succinate; vii) tartrate; viii) lactate; ix) alkyl        sulfates: Alk-O—S(O)O⁻ such as methyl sulfate and ethyl        sulfate; x) aryl sulfates: Ar—O—S(O)O⁻ such as benzene sulfate        and toluene sulfate; xi) alkoxy sulfates: Alk-O—S(O)₂O⁻ such as        methoxy sulfate and ethoxy sulfate; xii) aryloxy sulfates:        Ar—O—S(O)₂O⁻, xiii) phosphates O═P(OH)₂—O⁻, O═P(O⁻)₂—OH        O═P(O⁻)₃, HO—[P(O)(O⁻)]_(w)—P(O)(O⁻)₂ with w being an        integer; xiv) acetate; xv) triflate; and xvi) borates such as        tetrafluoroborate, xvii) disulfate (O═)₂S(O—)₂ or SO₄ ²⁻ and        monosulfate HSO₄ ⁻;    -    the anionic counterion, derived from the organic or mineral        acid salt, ensures the electrical neutrality of the molecule;        thus, it is understood that when the anion comprises several        anionic charges, then the same anion may serve for the        electrical neutrality of several cationic groups in the same        molecule or else may serve for the electrical neutrality of        several molecules; for example, a disulfide dye of formula (I)        which contains two cationic chromophores may contain either two        “singly charged” anionic counterions or a “doubly charged”        anionic counterion such as (O═)₂S(O⁻)₂ or O═P(O⁻)₂—OH;    -   Moreover, the addition salts that may be used in the context of        the invention are especially chosen from addition salts with a        cosmetically acceptable base such as basifying agents as defined        below, for instance alkali metal hydroxides such as sodium        hydroxide, potassium hydroxide, aqueous ammonia, amines or        alkanolamines.    -   the term “at least one” is equivalent to the term “one or more”;        and    -   the term “inclusive” for a range of concentrations means that        the limits of that range are included in the defined range.        1). The Composition of the Invention

The composition according to the invention is cosmetic, i.e. it is in acosmetic medium and comprises:

-   -   i) at least one cationic direct dye bearing a disulfide        function, a thiol function or a protected-thiol function;    -   ii) at least one nonionic surfactant;    -   iii) at least one amphoteric surfactant;    -   iv) at least one alkaline agent; and    -   v) at least one reducing agent.        The Cosmetic Medium:

The term “cosmetic medium” means a medium that is suitable for dyeingkeratin fibres, also known as a dye support, which is a cosmetic mediumgenerally formed from water or a mixture of water and one or moreorganic solvents or a mixture of organic solvents. Preferably, thecomposition comprises water in a content especially inclusively between5% and 95% relative to the total weight of the composition.

The term “organic solvent” means an organic substance that is capable ofdissolving another substance without chemically modifying it.

Organic Solvents:

Examples of organic solvents that may be mentioned include C₁-C₄ loweralkanols, such as ethanol and isopropanol; polyols and polyol ethers,for instance 2-butoxyethanol, propylene glycol, propylene glycolmonomethyl ether, diethylene glycol monoethyl ether and monomethylether, and also aromatic alcohols, for instance benzyl alcohol orphenoxyethanol, and mixtures thereof.

The organic solvents are preferably present in proportions preferablyinclusively between 0.1% and 40% by weight relative to the total weightof the dye composition, more preferentially between 1% and 30% by weightapproximately and even more preferentially inclusively between 5% and25% by weight relative to the total weight of the composition.

i) Direct Dyes Bearing a Disulfide or Thiol Function of the Invention:

The direct dye(s) bearing a disulfide, thiol or protected-thiol functionused in the invention are of formula (I) as defined previously.

According to one particular mode of the invention, the dyes (I) aredisulfide dyes, i.e. for which U represents the following radical a)—S—C′_(sat)—(X′)_(p′)-A′, and more particularly the dyes of formula (I)are symmetrical, i.e. they are such that A=A′, C_(sat)=C′_(sat), X=X′and p=p′.

According to another particular mode of the invention, the dyes offormula (I) bearing a thiol function are as defined previously, i.e. Urepresenting the radical b) Y.

Another particular embodiment of the invention relates to fluorescentdyes bearing a disulfide, thiol or protected-thiol function.

-   -   i).1) Y:

According to one particular embodiment of the invention, the direct dyeof formula (I) is a thiol dye, i.e. Y represents i) a hydrogen atom.

In accordance with another particular embodiment of the invention, inthe abovementioned formula (I), Y is a protecting group known to thoseskilled in the art, for instance those described in the publications“Protective Groups in Organic Synthesis”, T. W. Greene, published byJohn Wiley & Sons, NY, 1981, pp. 193-217; “Protecting Groups”, P.Kocienski, Thieme, 3rd edition, 2005, chapter 5, and Ullmann'sEncyclopedia, “Peptide Synthesis”, pp. 4-5, 2005 Wiley-VCH Verlag GmbH &Co. KGaA, Weinheim 10.1002/14356007.a19 157;

In particular, Y represents a thiol-function protecting group chosenfrom the following radicals:

-   -   (C₁-C₄)alkylcarbonyl;    -   (C₁-C₄)alkylthiocarbonyl;    -   (C₁-C₄)alkoxycarbonyl;    -   (C₁-C₄)alkoxythiocarbonyl;    -   (C₁-C₄)alkylthio-thiocarbonyl;    -   (di)(C₁-C₄)(alkyl)aminocarbonyl;    -   (di)(C₁-C₄)(alkyl)aminothiocarbonyl;    -   arylcarbonyl, for instance phenylcarbonyl;    -   aryloxycarbonyl;    -   aryl(C₁-C₄)alkoxycarbonyl;    -   (di)(C₁-C₄)(alkyl)aminocarbonyl, for instance        dimethylaminocarbonyl;    -   (C₁-C₄)(alkyl)arylaminocarbonyl;    -   carboxyl;    -   SO₃ ⁻; M⁺ with M⁺ representing an alkali metal such as sodium or        potassium, or alternatively a counterion of the cationic        chromophore A and M⁺ are absent;    -   optionally substituted aryl such as phenyl, dibenzosuberyl or        1,3,5-cycloheptatrienyl;        -   optionally substituted heteroaryl; especially including the            following cationic or non-cationic heteroaryl radicals            comprising from 1 to 4 heteroatoms:            -   i) 5-, 6- or 7-membered monocyclic radicals such as                furanyl or furyl, pyrrolyl or pyrryl, thiophenyl or                thienyl, pyrazolyl, oxazolyl, oxazolium, isoxazolyl,                isoxazolium, thiazolyl, thiazolium, isothiazolyl,                isothiazolium, 1,2,4-triazolyl, 1,2,4-triazolium,                1,2,3-triazolyl, 1,2,3-triazolium, 1,2,4-oxazolyl,                1,2,4-oxazolium, 1,2,4-thiadiazolyl,                1,2,4-thiadiazolium, pyrylium, thiopyridyl, pyridinium,                pyrimidinyl, pyrimidinium, pyrazinyl, pyrazinium,                pyridazinyl, pyridazinium, triazinyl, triazinium,                tetrazinyl, tetrazinium, azepine, azepinium, oxazepinyl,                oxazepinium, thiepinyl, thiepinium, imidazolyl,                imidazolium;            -   ii) 8- to 11-membered bicyclic radicals such as indolyl,                indolinium, benzimidazolyl, benzimidazolium,                benzoxazolyl, benzoxazolium, dihydrobenzoxazolinyl,                benzothiazolyl, benzothiazolium, pyridoimidazolyl,                pyridoimidazolium, thienocycloheptadienyl, these                monocyclic or bicyclic groups being optionally                substituted with one or more groups such as                (C₁-C₄)alkyl, for instance methyl, or                polyhalo(C₁-C₄)alkyl, for instance trifluoromethyl;            -   iii) or the following tricyclic ABC radical:

-   -   -   -    in which the two rings A and C optionally comprise a                heteroatom, and ring B is a 5-, 6- or 7-membered ring,                particularly a 6-membered ring, and contains at least                one heteroatom, for instance piperidyl or pyranyl;

        -   optionally cationic, optionally substituted            heterocycloalkyl, the heterocycloalkyl group especially            represents a saturated or partially saturated 5-, 6- or            7-membered monocyclic group comprising from 1 to 4            heteroatoms chosen from oxygen, sulfur and nitrogen, such as            di/tetrahydrofuryl, di/tetrahydrothiophenyl,            di/tetrahydropyrrolyl, di/tetrahydropyranyl,            di/tetra/hexahydrothiopyranyl, dihydropyridyl, piperazinyl,            piperidinyl, tetramethylpiperidyl, morpholinyl,            di/tetra/hexahydroazepinyl, di/tetrahydropyrimidinyl, these            groups being optionally substituted with one or more groups            such as (C₁-C₄)alkyl, oxo or thioxo; or the heterocycle            represents the following group:

-   -   -    in which R′^(c), R′^(d), R′^(e), R′^(f), R′^(g) and R′^(h),            which may be identical or different, represent a hydrogen            atom or a (C₁-C₄)alkyl group, or alternatively two groups            R′^(g) with R′^(h), and/or R′^(e) with R′^(f), form an oxo            or thioxo group, or alternatively R′^(g) with R′^(e)            together form a cycloalkyl; and v represents an integer            between 1 and 3 inclusive; preferentially, R′^(c) to R′^(h)            represent a hydrogen atom; and An′″⁻ represents a            counterion;        -   —C(NR′^(c)R′^(d))═N⁺R′^(e)R′^(f); An′″⁻ with R′^(c), R′^(d),            R′^(e) and R′^(f), which may be identical or different,            representing a hydrogen atom or a (C₁-C₄)alkyl group;            preferentially, R′^(c) to R′^(f) represent a hydrogen atom;            and An′″⁻ represents a counterion;        -   —C(NR′^(c)R′^(d))═NR′^(e); with R′^(c), R′^(d) and R′^(e) as            defined previously;        -   optionally substituted (di)aryl(C₁-C₄)alkyl such as            9-anthracenylmethyl, phenylmethyl or diphenylmethyl            optionally substituted with one or more groups especially            chosen from (C₁-C₄)alkyl, (C₁-C₄)alkoxy such as methoxy,            hydroxyl, alkylcarbonyl or (di)(C₁-C₄)(alkyl)amino such as            dimethylamino;        -   optionally substituted (di)heteroaryl(C₁-C₄)alkyl, the            heteroaryl group especially being a cationic or noncationic,            5- or 6-membered monocyclic radical comprising from 1 to 4            heteroatoms chosen from nitrogen, oxygen and sulfur, such as            pyrrolyl, furanyl, thiophenyl, pyridyl, pyridyl N-oxide such            as 4-pyridyl or 2-pyridyl-N-oxide, pyrylium, pyridinium or            triazinyl groups, optionally substituted with one or more            groups such as alkyl, particularly methyl; advantageously,            the (di)heteroaryl(C₁-C₄)alkyl is (di)heteroarylmethyl or            (di)heteroarylethyl;        -   CR¹R²R³ with R¹, R² and R³, which may be identical or            different, representing a halogen atom or a group chosen            from:            -   (C₁-C₄)alkyl;            -   (C₁-C₄)alkoxy;            -   optionally substituted aryl such as phenyl optionally                substituted with one or more groups, for instance                (C₁-C₄)alkyl, (C₁-C₄)alkoxy or hydroxyl;            -   optionally substituted heteroaryl such as thiophenyl,                furanyl, pyrrolyl, pyranyl or pyridyl, optionally                substituted with a (C₁-C₄)alkyl group;            -   P(Z¹)R′¹R′²R′³ with R′¹ and R′², which may be identical                or different, representing a hydroxyl, (C₁-C₄)alkoxy or                alkyl group, R′³ representing a hydroxyl or                (C₁-C₄)alkoxy group, and Z¹ representing an oxygen or                sulfur atom;        -   a sterically hindered ring; and        -   optionally substituted alkoxyalkyl, such as methoxymethyl            (MOM), ethoxyethyl (EOM) and isobutoxymethyl.

According to one particular embodiment, the thiol-protected dyes offormula (I) comprise a group Y chosen from i) aromatic cationic 5- or6-membered monocyclic heteroaryl comprising from 1 to 4 heteroatomschosen from oxygen, sulfur and nitrogen, such as oxazolium, isoxazolium,thiazolium, isothiazolium, 1,2,4-triazolium, 1,2,3-triazolium,1,2,4-oxazolium, 1,2,4-thiadiazolium, pyrylium, pyridinium,pyrimidinium, pyrazinyl, pyrazinium, pyridazinium, triazinium,tetrazinium, oxazepinium, thiepinyl, thiepinium, imidazolium; ii)cationic 8- to 11-membered bicyclic heteroaryl such as indolinium,benzimidazolium, benzoxazolium, benzothiazolium, these monocyclic orbicyclic heteroaryl groups optionally being substituted with one or moregroups such as alkyls, for instance methyl, or polyhalo(C₁-C₄)alkyl suchas trifluoromethyl; iii) or the following heterocyclic:

in which R′^(c) and R′^(d), which may be identical or different,represent a hydrogen atom or a group (C₁-C₄)alkyl; preferentially R′^(c)to R′^(d) represent a group (C₁-C₄)alkyl such as methyl; and An′″⁻represents a counterion.

In particular, Y represents a group chosen from oxazolium, isoxazolium,thiazolium, isothiazolium, 1,2,4-triazolium, 1,2,3-triazolium,1,2,4-oxazolium, 1,2,4-thiadiazolium, pyrylium, pyridinium,pyrimidinium, pyrazinium, pyridazinium, triazinium and imidazolium,benzimidazolium, benzoxazolium, benzothiazolium, these groups beingoptionally substituted with one or more (C₁-C₄)alkyl groups, especiallymethyl.

In particular, Y represents a protecting group such as:

-   -   (C₁-C₄)alkylcarbonyl, for instance methylcarbonyl or        ethylcarbonyl;    -   arylcarbonyl, for instance phenylcarbonyl;    -   (C₁-C₄)alkoxycarbonyl;    -   aryloxycarbonyl;    -   aryl(C₁-C₄)alkoxycarbonyl;    -   (di)(C₁-C₄)(alkyl)aminocarbonyl, for instance        dimethylaminocarbonyl;    -   (C₁-C₄)(alkyl)arylaminocarbonyl;    -   optionally substituted aryl such as phenyl;    -   5- or 6-membered monocyclic heteroaryl such as imidazolyl or        pyridyl;    -   cationic 5- or 6-membered monocyclic heteroaryl such as        pyrylium, pyridinium, pyrimidinium, pyrazinium, pyridazinium,        triazinium, imidazolium; these groups being optionally        substituted with one or more identical or different (C₁-C₄)alkyl        groups such as methyl;    -   cationic 8- to 11-membered bicyclic heteroaryl such as        benzimidazolium or benzoxazolium; these groups being optionally        substituted with one or more identical or different (C₁-C₄)alkyl        groups such as methyl;    -   cationic heterocycle having the following formula:

-   -   —C(NH₂)═N⁺H₂; An′″⁻; with An′″⁻ being an anionic counterion as        defined previously;    -   —C(NH₂)═NH;    -   SO₃ ⁻, M⁺ with M⁺ representing an alkali metal such as sodium or        potassium.

i).2) C_(sat) and C′_(sat):

As indicated previously, in formula (I), C_(sat) and C′_(sat),independently of each other, represent a linear or branched or cyclic,optionally substituted C₁-C₁₈ alkylene chain.

Substituents that may be mentioned include the following groups: i)amino, ii) (C₁-C₄)alkylamino, iii) (C₁-C₄)dialkylamino, or the group iv)R^(a)—Z^(a)—C(Z^(b))—Z^(c)—, in which Z^(a), Z^(b), which may beidentical or different, represent an oxygen or sulfur atom, or a groupNR^(a)′, Z^(c), representing a bond, an oxygen or sulfur atom or a groupNR^(a) and R^(a), represents an alkali metal, a hydrogen atom or a C₁-C₄alkyl group and R^(a)′ represents a hydrogen atom or a C₁-C₄ alkylgroup; more particularly, the groups iv) are chosen from carboxylate—C(O)O⁻ or —C(O)OMetal (Metal=alkali metal), carboxyl —C(O)—OH,guanidino H₂H—C(NH₂)—NH—, amidino H₂H—C(NH₂)—, (thio)ureo H₂N—C(O)—NH—and H₂N—C(S)—NH—, aminocarbonyl —C(O)—NRa′₂ or aminothiocarbonyl—C(S)—NRa′₂; carbamoyl Ra′—C(O)—NRa′— or thiocarbamoyl Ra′—C(S)—NRa′—with Ra′, which may be identical or different, representing a hydrogenatom or a (C₁-C₄)alkyl group; the said substituent(s) are preferablypresent on the carbon in the beta or gamma position relative to thesulfur atoms of the disulfide, thiol or protected-thiol group.

Preferably, in the case of formula (I), C_(sat) and C′_(sat) represent achain —(CH₂)_(k)— with k being an integer between 1 and 8 inclusive.

i).3) X and X′:

In accordance with one particular embodiment of the invention, in theabove-mentioned formula (I), when p and p′ is equal to 1, the radicals Xand X′, which may be identical or different, represent the followingsequence:-(T)_(t)-(Z)_(z)-(T′)_(t′)-the said sequence being linked in formula (I) symmetrically as follows:C_(sat)(or C′_(sat))-(T)_(t)-(Z)_(z)-(A or A′);in which:

-   -   T and T′, which may be identical or different, represent one or        more radicals or combinations thereof chosen from: —O—; —S—;        —N(R)—; —N+(R)(R^(o))—; —S(O)—; —S(O)₂—; —C(O)—; with R, R^(°),        which may be identical or different, representing a hydrogen        atom, a C₁-C₄ alkyl radical, C₁-C₄ hydroxyalkyl radical or an        aryl(C₁-C₄)alkyl radical; and a cationic or non-cationic,        preferentially monocyclic heterocycloalkyl or heteroaryl        radical, preferentially containing two heteroatoms (more        preferentially two nitrogen atoms) and preferentially being 5-        to 7-membered, more preferentially imidazolium;    -    the indices t and t′, which may be identical or different, are        equal to 0 or 1;    -   Z represents:        -   —(CH₂)_(m)— radical with m being an integer between 1 and 8;        -   —(CH₂CH₂O)_(q)— or —(OCH₂CH₂)_(q)— in which q is an integer            between 1 and 5 inclusive;        -   an aryl, alkylaryl or arylalkyl radical in which the alkyl            radical is C₁-C₄ and the aryl radical is preferably C₆,            being optionally substituted with at least one group SO₃M            with M representing a hydrogen atom, an alkali metal or an            ammonium group substituted with one or more identical or            different, linear or branched C₁-C₁₈ alkyl radicals            optionally bearing at least one hydroxyl;    -   z is 0 or 1.

Moreover, according to one particular embodiment of the invention, Zrepresents:

-   -   in which M represents a hydrogen atom, an alkali metal or an        ammonium group or an ammonium group substituted with one or more        identical or different, linear or branched C₁-C₁₀ alkyl radicals        optionally bearing at least one hydroxyl; 0-4 represents an        integer between 0 and 4 inclusive, and q represents an integer        between 1 and 6.

i).4). A and A′:

The radicals A and/or A′ of formula (I) contain at least one quaternizedcationic chromophore or at least one chromophore bearing a quaternizedor quaternizable cationic group.

According to one preferred embodiment of the invention, the dyes (I)according to the invention are disulfides and comprise identical,preferably quaternized cationic chromophores A and A′.

More particularly, the dyes of formula (I) according to the inventionare symmetrical disulfides, i.e. they contain a C₂ axis of symmetry,i.e. formula (I) is such that:A-(X)_(p)—C_(sat)—S—S—C′_(sat)—(X′)_(p′)-A′ with A=A′, X═X′, p=p′,C_(sat)=C′_(sat).

As chromophores that are useful in the present invention, mention may bemade of those derived from the following dyes: acridines; acridones;anthranthrones; anthrapyrimidines; anthraquinones; azines; (poly)azos,hydrazono or hydrazones, in particular arylhydrazones; azomethines;benzanthrones; benzimidazoles; benzimidazolones; benzindoles;benzoxazoles; benzopyrans; benzothiazoles; benzoquinones; bisazines;bis-isoindolines; carboxanilides; coumarins; cyanins such asazacarbocyanins, diazacarbocyanins, diazahemicyanins, hemicyanins, ortetraazacarbocyanins; diazines; diketopyrrolopyrroles; dioxazines;diphenylamines; diphenylmethanes; dithiazines; flavonoids such asflavanthrones and flavones; fluorindines; formazans; indamines;indanthrones; indigoids and pseudo-indigoids; indophenols; indoanilines;isoindolines; isoindolinones; isoviolanthrones; lactones; (poly)methinessuch as dimethines of stilbene or styryl type; naphthalimides;naphthanilides; naphtholactams; naphthoquinones; nitro, especiallynitro(hetero)aromatics; oxadiazoles; oxazines; perilones; perinones;perylenes; phenazines; phenoxazine; phenothiazines; phthalocyanin;polyenes/carotenoids; porphyrins; pyranthrones; pyrazolanthrones;pyrazolones; pyrimidinoanthrones; pyronines; quinacridones; quinolines;quinophthalones; squaranes; tetrazoliums; thiazines, thioindigo;thiopyronines; triarylmethanes, or xanthenes.

Among the cationic azo chromophores, mention may be made particularly ofthose derived from the cationic dyes described in the Kirk OthmerEncyclopedia of Chemical Technology, “Dyes, Azo”, J. Wiley & Sons,updated on Apr. 19, 2010.

Among the cationic azo chromophores A and/or A′ which can be usedaccording to the invention, mention may be made of the radicals derivedfrom the cationic azo dyes described in patent applications WO 95/15144,WO-95/01772 and EP-714954.

According to one preferred embodiment of the invention, the colouredchromophore A and/or A′ is chosen from cationic chromophores,preferentially those derived from dyes known as “basic dyes”.

Among the azo chromophores, mention may be made of those described inthe Colour Index International 3rd edition, and especially the followingcompounds:

-   -   Basic Red 22    -   Basic Red 76    -   Basic Yellow 57    -   Basic Brown 16    -   Basic Brown 17

Among the cationic quinone chromophores A and/or A′, those mentioned inthe abovementioned Colour Index International are suitable for use, andamong those, mention may be made, inter alia, of the radicals derivedfrom the following dyes:

-   -   Basic Blue 22    -   Basic Blue 99

Among the cationic azine chromophores A and/or A′, those listed in theColour Index International are suitable for use, and among those, forexample the radicals derived from the following dyes:

-   -   Basic Blue 17    -   Basic Red 2.

Among the cationic triarylmethane chromophores A and/or A′ that may beused according to the invention, mention may be made, besides thoselisted in the Colour Index, of the radicals derived from the followingdyes:

-   -   Basic Green 1    -   Basic Violet 3    -   Basic Violet 14    -   Basic Blue 7    -   Basic Blue 26.

Mention may also be made of the cationic chromophores derived from thedyes described in documents U.S. Pat. No. 5,888,252, EP 1 133 975, WO03/029 359, EP 860 636, WO 95/01772, WO 95/15144 and EP 714 954. Mentionmay also be made of those listed in the encyclopaedia “The chemistry ofsynthetic dye” by K. Venkataraman, 1952, Academic press vol. 1 to 7, inKirk Othmer's encyclopaedia “Chemical technology”, in the chapter 40“Dyes and dye intermediates”, 1993, Wiley and sons, and in variouschapters of “Ullmann's encyclopedia of Industrial chemistry” 7thedition, Wiley and sons.

Preferably, the chromophores A and/or A′ are chosen from those derivedfrom dyes of azo and hydrazono type.

According to one particular embodiment, the cationic radicals A and/orA′ in formula (I) comprise at least one cationic azo chromophore derivedfrom a dye described in EP 850 636, FR 2 788 433, EP 920 856, WO99/48465, FR 2 757 385, EP 85/0637, EP 91/8053, WO 97/44004, FR 2 570946, FR 2 285 851, DE 2 538 363, FR 2 189 006, FR 1 560 664, FR 1 540423, FR 1 567 219, FR 1 516 943, FR 1 221 122, DE 4 220 388, DE 4 137005, WO 01/66646, U.S. Pat. No. 5,708,151, WO 95/01772, WO 51/5144, GB 1195 386, U.S. Pat. No. 3,524,842, U.S. Pat. No. 5,879,413, EP 1 062 940,EP 1 133 976, GB 738 585, DE 2 527 638, FR 2 275 462, GB 1974-27645,Acta Histochem. (1978), 61 (1), 48-52; Tsitologiya (1968), 10 (3),403-5; Zh. Obshch. Khim. (1970), 40 (1), 195-202; Ann. Chim. (Rome)(1975), 65 (5-6), 305-14; Journal of the Chinese Chemical Society(Taipei) (1998), 45 (1), 209-211; Rev. Roum. Chim. (1988), 33 (4),377-83; Text. Res. J. (1984), 54 (2), 105-7; Chim. Ind. (Milan) (1974),56 (9), 600-3; Khim. Tekhnol. (1979), 22 (5), 548-53; Ger. Monatsh.Chem. (1975), 106 (3), 643-8; MRL Bull. Res. Dev. (1992), 6 (2), 21-7;Lihua Jianyan, Huaxue Fence (1993), 29 (4), 233-4; Dyes Pigm. (1992), 19(1), 69-79; Dyes Pigm. (1989), 11 (3), 163-72.

According to one variant, A and/or A′ of formula (I) contain at leastone cationic radical borne by, or included in, at least one of thechromophores.

Preferably, the cationic radical is a quaternary ammonium; morepreferentially, the cationic charge is endocyclic.

These cationic radicals are, for example, a cationic radical:

-   -   bearing an exocyclic (di/tri)(C₁-C₈)alkylammonium charge, or    -   bearing an endocyclic charge, such as the following cationic        heteroaryl groups: acridinium, benzimidazolium,        benzobistriazolium, benzopyrazolium, benzopyridazinium,        benzoquinolium, benzothiazolium, benzotriazolium, benzoxazolium,        bipyridinium, bis-tetrazolium, dihydrothiazolium,        imidazopyridinium, imidazolium, indolium, isoquinolium,        naphthoimidazolium, naphthoxazolium, naphthopyrazolium,        oxadiazolium, oxazolium, oxazolopyridinium, oxonium,        phenazinium, phenoxazolium, pyrazinium, pyrazolium,        pyrazoyltriazolium, pyridinium, pyridinoimidazolium, pyrrolium,        pyrylium, quinolium, tetrazolium, thiadiazolium, thiazolium,        thiazolopyridinium, thiazoylimidazolium, thiopyrylium,        triazolium or xanthylium.

Mention may be made of the hydrazono cationic chromophores of formulae(II) and (III′), and the azo cationic chromophores (IV), (IV′), (V) and(V′) below:(*)-Het⁺-C(R^(a))═N—N(R^(b))—Ar,Q⁻  (II)Q⁻,Het⁺-C(R^(a))═N—N(R^(b))—Ar′-(*),  (II′)(*)-Het⁺-N(R^(a))—N═C(R^(b))—Ar,Q⁻  (III)Q⁻,Het⁺-N(R^(a))—N═C(R^(b))—Ar′-(*),  (III′)(*)-Het⁺-N═N—Ar,Q⁻  (IV)Q⁻,Het⁺-N═N—Ar′-(*),  (IV′)(*)-Ar⁺—N═N—Ar″,Q⁻  (V)Q⁻,Ar⁺—N═N—Ar″-(*)  (V′)formulae (II) to (V′) with:

-   -   Het⁺ representing a cationic heteroaryl radical, preferentially        bearing an endocyclic cationic charge, such as imidazolium,        indolium or pyridinium, optionally substituted, preferentially        with one or more (C₁-C₈) alkyl groups such as methyl;    -   Ar⁺ represents an aryl radical, such as phenyl or naphthyl,        bearing an exocyclic cationic charge, preferentially ammonium,        particularly tri(C₁-C₈)alkylammonium such as trimethylammonium;    -   Ar represents an aryl group, especially phenyl, optionally        substituted, preferentially with one or more electron-donating        groups such as i) optionally substituted (C₁-C₈)alkyl, ii)        optionally substituted (C₁-C₈)alkoxy, iii)        (di)(C₁-C₈)(alkyl)amino optionally substituted on the alkyl        group(s) with a hydroxyl group, iv) aryl(C₁-C₈)alkylamino, v)        optionally substituted N—(C₁-C₈)alkyl-N-aryl(C₁-C₈)alkylamino or        alternatively Ar represents a julolidine group;    -   Ar′ is an optionally substituted divalent (hetero)arylene group        such as phenylene, particularly para-phenylene, or naphthalene,        which are optionally substituted, preferentially with one or        more groups (C₁-C₈)alkyl, hydroxyl or (C₁-C₈)alkoxy;    -   Ar″ is an optionally substituted (hetero)aryl group such as        phenyl or pyrazolyl, which are optionally substituted,        preferentially with one or more groups (C₁-C₈)alkyl, hydroxyl,        (di)(C₁-C₈)(alkyl)amino, (C₁-C₈)alkoxy or phenyl;    -   R^(a) and R^(b), which may be identical or different, represent        a hydrogen atom or a group (C₁-C₈)alkyl, which is optionally        substituted, preferentially with a hydroxyl group; or        alternatively the substituent R^(a) with a substituent of Het⁺        and/or R^(b) with a substituent of Ar form, together with the        atoms that bear them, a (hetero)cycloalkyl; particularly, R^(a)        and R^(b) represent a hydrogen atom or a group (C₁-C₄)alkyl,        which is optionally substituted with a hydroxyl group;    -   Q⁻ represents an organic or mineral anionic counterion such as a        halide or an alkyl sulfate;    -   (*) represents the part of the chromophore linked to the rest of        the molecule of formula (I).

In particular, mention may be made of the azo and hydrazono chromophoresbearing an endocyclic cationic charge of formulae (II) to (IV′) asdefined previously. More particularly those of formulae (II) to (IV′)derived from the dyes described in patent applications WO 95/15144, WO95/01772 and EP-714954. Preferentially the following chromophores:

formulae (III-1) and (IV-1) with:

-   -   R¹ representing a group (C₁-C₄)alkyl such as methyl;    -   R² and R³, which may be identical or different, representing a        hydrogen atom or a group (C₁-C₄)alkyl such as methyl; and    -   R⁴ representing a hydrogen atom or an electron-donating group        such as optionally substituted (C₁-C₈)alkyl, optionally        substituted (C₁-C₈)alkoxy, or (di)(C₁-C₈)(alkyl)amino optionally        substituted on the alkyl group(s) with a hydroxyl group;        particularly, R⁴ is a hydrogen atom,    -   Z represents a group CH or a nitrogen atom, preferentially CH,    -   Q⁻ is as defined previously;        it being understood that the chromophore (II-1) or (IV-1) is        linked to the rest of the molecule of formula (I) by R², R¹ or        R⁴ in which case one of the hydrogen atoms of R², R¹ or R⁴ is        substituted with X or X′ if p=1 or p′=1 or alternatively with        C_(sat) or C_(sat′) if p=0 or p′=0.

Particularly, the chromophores (II-1) and (IV-1) are derived from BasicRed 51, Basic Yellow 87 and Basic Orange 31 or derivatives thereof:

with Q′ being an anionic counterion as defined previously, particularlya halide such as chloride or an alkyl sulfate such as methyl sulfate ormesityl.

According to one particular embodiment of the invention, the dyes offormula (I) are fluorescent, i.e. they contain at least one fluorescentchromophore as defined previously.

As fluorescent chromophores A and/or A′ that are useful in the presentinvention, mention may be made of radicals derived from the followingdyes: acridines, acridones, benzanthrones, benzimidazoles,benzimidazolones, benzindoles, benzoxazoles, benzopyrans,benzothiazoles, coumarins,difluoro{2-[(2H-pyrrol-2-ylidene-kN)methyl]-1H-pyrrolato-kN}bores(BODIPY®), diketopyrrolopyrroles, fluorindines, (poly)methines(especially cyanins and styryls/hemicyanins), naphthalimides,naphthanilides, naphthylamine (such as dansyls), oxadiazoles, oxazines,perilones, perinones, perylenes, polyenes/carotenoids, squaranes,stilbenes and xanthenes.

Mention may also be made of the fluorescent dyes A and/or A′ describedin documents EP 1 133 975, WO 03/029 359, EP 860 636, WO 95/01772, WO95/15144, EP 714 954 and those listed in the encyclopaedia The chemistryof synthetic dyes by K. Venkataraman, 1952, Academic Press, vol. 1 to 7,in Kirk Othmer's encyclopaedia Chemical Technology, in the chapter “Dyesand dye intermediates”, 1993, Wiley and Sons, and in various chapters ofUllmann's Encyclopedia of Industrial Chemistry 7th edition, Wiley andSons, and in The Handbook—A Guide to Fluorescent Probes and LabelingTechnologies, 10th Ed Molecular Probes/Invitrogen—Oregon 2005 circulatedon the Internet or in the preceding printed editions.

According to one preferred variant of the invention, the fluorescentchromophore A and/or A′ is cationic and comprises at least onequaternary ammonium radical such as those derived from the polymethinedyes of formulae (VI) and (VI′) below:W⁺—[C(R^(c))═C(R^(d))]_(m′)—Ar′-(*)Q⁻  (VI)Ar—[C(R^(d))═C(R^(c))]_(m′)—W′⁺-(*)Q⁻  (VI′)formula (VI) or (VI′) with:

-   -   W⁺ representing a cationic heterocyclic or heteroaryl group,        particularly comprising a quaternary ammonium optionally        substituted with one or more groups (C₁-C₈)alkyl optionally        substituted especially with one or more hydroxyl groups;    -   W′⁺ representing a divalent heterocyclic or heteroaryl radical        as defined for W⁺;    -   Ar representing an aryl group such as phenyl or naphthyl,        optionally substituted preferentially with i) one or more        halogen atoms such as chlorine or fluorine; ii) one or more        groups (C₁-C₈)alkyl, preferably of C₁-C₄ such as methyl; iii)        one or more hydroxyl groups; iv) one or more (C₁-C₈)alkoxy        groups such as methoxy; v) one or more hydroxy(C₁-C₈)alkyl        groups such as hydroxyethyl, vi) one or more amino groups or        (di)(C₁-C₈)alkylamino, preferably with the C₁-C₄ alkyl part        optionally substituted with one or more hydroxyl groups, such as        (di)hydroxyethylamino, vii) with one or more acylamino        groups; viii) one or more heterocycloalkyl groups such as        piperazinyl, piperidyl or 5- or 6-membered heteroaryl such as        pyrrolidinyl, pyridyl and imidazolinyl;    -   Ar′ is a divalent aryl radical as defined for Ar;    -   m′ represents an integer between 1 and 4 inclusive, and in        particular m is 1 or 2; more preferentially 1;    -   R^(c) and R^(d), which may be identical or different, represent        a hydrogen atom or an optionally substituted group (C₁-C₈)alkyl,        preferentially of C₁-C₄, or alternatively R^(c) contiguous with        W⁺ or W′⁺ and/or R^(d) contiguous with Ar or Ar′ form, with the        atoms that bear them, a (hetero)cycloalkyl, particularly R^(c)        is contiguous with W⁺ or W′⁺ and forms a (hetero)cycloalkyl such        as cyclohexyl;    -   Q⁻ is an organic or mineral anionic counterion as defined        previously;    -   (*) represents the part of the chromophore linked to the rest of        the molecule of formula (I).

According to another variant, the disulfide, thiol or protected-thioldye is a quaternized or quaternizable fluorescent dye such that, informula (I) with p and p′ equal to 1 and A and/or A′ representing anaphthalimidyl radical optionally bearing an exocyclic cationic chargeof formula (VII) or (VII′):

in which formulae (VII) and (VII′):

-   -   R^(e), R^(f), R^(g) and R^(h), which may be identical or        different, representing a hydrogen atom or a (C₁-C₆)alkyl group        which is optionally substituted, preferentially with a        di(C₁-C₆)alkylamino or tri(C₁-C₆)alkylammonium group such as        trimethylammonium;

-   -   representing the bond which links the naphthalimidyl radical to        the rest of the molecule via X or X′, if p=1 or p′=1 or        alternatively via C_(sat) or C_(sat′) if p=0 or p′=0.

According to one embodiment of the invention, p=1, z=t′=0, t=1 and Trepresents —N(R)—, preferably in the para position on Ar relative to theolefin function —C(R^(c))═C(R^(d))—.

Particularly, in one variant, p=1, z=t′=0, t=1 and T represents —N(R)—,preferably in the para position on Ar relative to the styryl function—C(Rc)=C(Rd)- and T′ represents a group —N(R)— or —N+(R)(R^(o))— or animidazolium.

Preferably, W⁺ or W′⁺ is an imidazolium, pyridinium, benzimidazolium,pyrazolium, benzothiazolium or quinolinium optionally substituted withone or more identical or different C₁-C₄ alkyl radicals.

According to one particularly preferred embodiment of the invention, Aand/or A′ represent the chromophore (VI′) as defined previously withm′=1, Ar representing a phenyl group substituted para to the styrylgroup —C(R^(d))═C(R^(c))— with a group (di)(hydroxy)(C₁-C₆)(alkyl)aminosuch as dihydroxy(C₁-C₄)alkylamino, and W′⁺ representing an imidazoliumor pyridinium group, preferentially ortho- or para-pyridinium.

As examples of dyes of the invention, mention may be made of thedisulfide dyes chosen from formulae (VIII) to (XIV) and the thiol orprotected-thiol dyes chosen from formulae (VIII′) to (XIV′) below:

in which formulae (VIII) to (XIV) and (VIII′) to (XIV′):

-   -   G and G′, which may be identical or different, represent a group        —NR_(c)R_(d), —NR′_(c)R′_(d) or C₁-C₆ alkoxy which is optionally        substituted, preferentially unsubstituted; preferentially, G and        G′ represent a group —NR_(c)R_(d) or —NR′_(c)R′_(d),        respectively;    -   R¹, R², R³ and R⁴, which may be identical or different,        represent a hydrogen atom or a C₁-C₆ alkyl group; preferentially        a hydrogen atom;    -   R_(a) and R′_(a), which may be identical or different, represent        an aryl(C₁-C₄)alkyl group or a C₁-C₆ alkyl group optionally        substituted with a hydroxyl or amino, C₁-C₄ alkylamino or C₁-C₄        dialkylamino group, the said alkyl radicals possibly forming,        with the nitrogen atom that bears them, a 5- to 7-membered        heterocycle, optionally comprising another nitrogen or        non-nitrogen heteroatom; preferentially, R_(a) and R′_(a)        represent a C₁-C₃ alkyl group optionally substituted with a        hydroxyl group, or a benzyl group;    -   R_(b) and R′_(b), which may be identical or different, represent        a hydrogen atom, an aryl(C₁-C₄)alkyl group or a C₁-C₆ alkyl        group that is optionally substituted; preferentially, R_(b) and        R′_(b) represent a hydrogen atom or a C₁-C₃ alkyl or benzyl        group;    -   R_(c), R′_(c), R_(d) and R′_(d), which may be identical or        different, represent a hydrogen atom, an aryl(C₁-C₄)alkyl or        C₁-C₆ alkoxy group or a C₁-C₆ alkyl group that is optionally        substituted; R_(c), R′_(c), R_(d) and R′_(d) preferentially        represent a hydrogen atom, a hydroxyl, C₁-C₃ alkoxy, amino or        C₁-C₃ (di)alkylamino group, or a C₁-C₃ alkyl group that is        optionally substituted with i) a hydroxyl group, ii) amino, iii)        C₁-C₃ (di)alkylamino, or iv) quaternary ammonium        (R″)(R′″)(R″″)N⁺—;    -    or alternatively two adjacent radicals R_(c) and R_(d), R′_(c)        and R′^(d) borne by the same nitrogen atom together form a        heterocyclic or heteroaryl group; preferentially, the        heterocycle or heteroaryl is monocyclic and 5- to 7-membered;        more preferentially, the groups are chosen from imidazolyl and        pyrrolidinyl;    -   R_(e) and R′_(e), which may be identical or different, represent        an optionally unsaturated linear or branched C₁-C₆ alkylene or        C₂-C₆ alkenylene hydrocarbon-based chain;    -   R_(f) and R′_(f), which may be identical or different, represent        a group di(C₁-C₄)alkylamino, a quaternary ammonium group        (R″)(R′″)(R″″)N⁺ in which R″, R′″ and R″″, which may be        identical or different, represent a hydrogen atom or a C₁-C₄        alkyl group or alternatively (R″)(R′″)(R″″)N⁺— represents an        optionally substituted cationic heteroaryl group, preferentially        an imidazolinium group optionally substituted with a C₁-C₃ alkyl        group;    -   R_(g), R′_(g), R″_(g), R′″_(g), R_(h), R′_(h), R″_(h), and        R′″_(h), which may be identical or different, represent a        hydrogen atom, a halogen atom, an amino, C₁-C₄ alkylamino, C₁-C₄        dialkylamino, cyano, carboxyl, hydroxyl or trifluoromethyl        group, an acylamino, C₁-C₄ alkoxy, (poly)hydroxy(C₂-C₄)alkoxy,        alkylcarbonyloxy, alkoxycarbonyl or alkylcarbonylamino radical,        an acylamino, carbamoyl or alkylsulfonylamino radical, an        aminosulfonyl radical, or a C₁-C₁₆ alkyl radical optionally        substituted with a group chosen from C₁-C₁₂ alkoxy, hydroxyl,        cyano, carboxyl, amino, C₁-C₄ alkylamino and C₁-C₄ dialkylamino,        or alternatively two alkyl radicals borne by the nitrogen atom        of the amino group form a 5- to 7-membered heterocycle        optionally comprising another nitrogen or non-nitrogen        heteroatom; preferentially, R_(g), R′_(g), R″_(g), R′″_(g),        R_(h), R′_(h), R″_(h), and R′″_(h) represent a hydrogen or        halogen atom or a C₁-C₃ alkyl group;    -   or alternatively two groups R_(g) and R′_(g); R″_(g) and        R′″_(g); R_(h), and R′_(h); R″_(h) and R′″_(h) borne by two        adjacent carbon atoms together form a benzo or indeno ring, a        fused heterocycloalkyl or fused heteroaryl group; the benzo,        indeno, heterocycloalkyl or heteroaryl ring being optionally        substituted with a halogen atom, an amino, C₁-C₄ alkylamino,        C₁-C₄ dialkylamino, nitro, cyano, carboxyl, hydroxyl or        trifluoromethyl group, an acylamino, C₁-C₄ alkoxy,        (poly)hydroxy(C₂-C₄)alkoxy, alkylcarbonyloxy, alkoxycarbonyl or        alkylcarbonylamino radical, an acylamino, carbamoyl or        alkylsulfonylamino radical, an aminosulfonyl radical, or a        C₁-C₁₆ alkyl radical optionally substituted with: a group chosen        from C₁-C₁₂ alkoxy, hydroxyl, cyano, carboxyl, amino, C₁-C₄        alkylamino, C₁-C₄ dialkylamino, or alternatively two alkyl        radicals borne by the nitrogen atom of the amino group form a 5-        to 7-membered heterocycle optionally comprising another nitrogen        or non-nitrogen heteroatom; preferentially, R_(g) and R′_(g);        R″_(g) and R′″_(g) together form a benzo group;    -   or alternatively two groups R_(i) and R_(g); R′″_(i) and        R′″_(g); R′_(i) and R′_(h); and/or R″_(i) and R″_(h) together        form a fused (hetero)cycloalkyl, preferentially cycloalkyl such        as cyclohexyl;    -   or alternatively when G represents —NR_(c)R_(d) and G′        represents —NR′_(c)R′_(d), two groups R_(c) and R′_(g); R′_(c)        and R″_(g); R_(d) and R_(g); R′_(d) and R′″_(g) together form a        saturated heteroaryl or heterocycle, optionally substituted with        one or more groups (C₁-C₆)alkyl, preferentially a 5- and        7-membered heterocycle containing one or two heteroatoms chosen        from nitrogen and oxygen; more preferentially the heterocycle is        chosen from morpholinyl, piperazinyl, piperidyl and pyrrolidinyl        groups;    -   R_(i), R′_(i), R″_(i), and R′″_(i), which may be identical or        different, represent a hydrogen atom or a C₁-C₄ alkyl group;    -   R₁, R₂, R₃, R₄, R′₁, R′₂, R′₃, and R′₄, which may be identical        or different, represent a hydrogen atom or a C₁-C₄ alkyl, C₁-C₁₂        alkoxy, hydroxyl, cyano, carboxyl, amino, C₁-C₄ alkylamino or        C₁-C₄ dialkylamino group, the said alkyl radicals possibly        forming with the nitrogen that bears them a 5- to 7-membered        heterocycle optionally comprising another nitrogen or        non-nitrogen heteroatom; preferentially, R₁, R₂, R₃, R₄, R′₁,        R′₂, R′₃, and R′₄ are hydrogen atoms or an amino group; more        preferentially, R₁, R₂, R₃, R₄, R′₁, R′₂, R′₃, and R′₄ represent        a hydrogen atom;    -   T_(a), T_(b), which may be identical or different, represent i)        either a covalent bond, ii) or one or more radicals or        combinations thereof chosen from —SO₂—, —O—, —S—, —N(R)—,        —N⁺(R)(R^(o))—, —CO—, with R, R^(o), which may be identical or        different, representing a hydrogen atom, a C₁-C₄ alkyl or C₁-C₄        hydroxyalkyl radical; or an aryl(C₁-C₄)alkyl, preferentially,        T_(a) is identical to T_(b) and represent a covalent bond or a        group chosen from —N(R)—, —C(O)—N(R)—, —N(R)—C(O)—, —O—C(O)—,        —C(O)—O— and —N⁺(R)(R^(o))—, with R, R^(o), which may be        identical or different, representing a hydrogen atom or a C₁-C₄        alkyl group; more preferentially, T_(a) and T_(b) represent a        bond; iii) or a cationic or non-cationic, preferentially        monocyclic, preferentially identical heterocycloalkyl or        heteroaryl radical, preferentially containing two heteroatoms        (more preferentially two nitrogen atoms) and preferentially        being 5- to 7-membered, such as imidazolium;

-   -   which may be identical or different, represent an optionally        group; preferentially, the heterocycles are identical,        monocyclic, saturated and 5- to 8-membered and comprise in total        two nitrogen atoms;

-   -   represent an aryl or heteroaryl group fused to the imidazolium        or phenyl ring; or alternatively is absent from the imidazolium        or phenyl ring; preferentially, when the ring is present, the        ring is a benzo;    -   m, m′, n and n′, which may be identical or different, represent        an integer between 0 and 6 inclusive, with m+n and m′+n′, which        may be identical or different, represents an integer between 1        and 10 inclusive; preferentially, m+n=m′+n′=an integer between 2        and 4 inclusive; more preferentially, m+n=m′+n′=an integer equal        to 2;    -   Y is as defined previously; in particular, Y represents a        hydrogen atom or a protecting group such as:        -   (C₁-C₄)alkylcarbonyl, for instance methylcarbonyl or            ethylcarbonyl;        -   arylcarbonyl, for instance phenylcarbonyl;        -   (C₁-C₄)alkoxycarbonyl;        -   aryloxycarbonyl;        -   aryl(C₁-C₄)alkoxycarbonyl;        -   (di)(C₁-C₄)(alkyl)aminocarbonyl, for instance            dimethylaminocarbonyl;        -   (C₁-C₄)(alkyl)arylaminocarbonyl;        -   optionally substituted aryl such as phenyl;        -   5- or 6-membered monocyclic heteroaryl such as imidazolyl or            pyridyl;        -   cationic 5- or 6-membered monocyclic heteroaryl such as            pyrylium, pyridinium, pyrimidinium, pyrazinium,            pyridazinium, triazinium, imidazolium; these groups being            optionally substituted with one or more identical or            different (C₁-C₄)alkyl groups such as methyl;        -   cationic 8- to 11-membered bicyclic heteroaryl such as            benzimidazolium or benzoxazolium; these groups being            optionally substituted with one or more identical or            different (C₁-C₄)alkyl groups such as methyl;        -   cationic heterocycle having the following formula:

-   -   -   —C(NH₂)═N⁺H₂; An′″⁻; with An′″⁻ being an anionic counterion            as defined previously;        -   —C(NH₂)═NH;        -   SO₃ ⁻, M⁺ with M⁺ representing an alkali metal such as            sodium or potassium; and

    -   M′ representing an anionic counterion, derived from a salt of an        organic or mineral acid, or from an organic or mineral base that        ensures the electrical neutrality of the molecule.

In particular, the dyes of formula (I) are chosen from dyes with anaphthalimidyl disulfide, thiol or protected-thiol chromophore, chosenfrom formulae (XIII), (XIII′), (XIV) and (XIV′) as defined previously.

According to one preferred mode of the invention, the dyes of formula(I) are chosen from disulfide, thiol or protected-thiol dyes chosen fromformulae (XV) to (XV′) below:

the organic or mineral acid salts, optical isomers, geometrical isomers,and solvates such as hydrates thereof;in which formulae (XV) and (XV′):

-   -   R and R′″, which may be identical or different, represent a        hydroxyl group, an amino group (NR_(a)R_(b)) or an ammonium        group (N⁺R_(a)R_(b)R_(c)), An⁻; preferentially hydroxyl; with        R_(a), R_(b) and R_(c), which may be identical or different,        representing a hydrogen atom or a (C₁-C₄)alkyl group;    -    or alternatively two alkyl groups R_(a) and R_(b) of the amino        or ammonium group form a 5- to 7-membered heterocycle optionally        comprising another nitrogen or non-nitrogen heteroatom, such as        morpholinyl, piperazinyl, piperidyl, pyrrolyl, morpholinium,        piperazinium, piperidinium or pyrrolinium, and An⁻ representing        an anionic counterion;    -   R′ and R″, which may be identical or different, represent a        hydrogen atom or a group as defined for R and R′″, respectively;    -   R_(g), R′_(g), R″_(g), R′″_(g), R_(h), R′_(h), R″_(h) and        R′″_(h), which may be identical or different, represent a        hydrogen or halogen atom, an amino, (di)(C₁-C₄)alkylamino,        cyano, carboxyl, hydroxyl, trifluoromethyl, acylamino, C₁-C₄        alkoxy, C₂-C₄ (poly)hydroxyalkoxy, (C₁-C₄)alkylcarbonyloxy,        (C₁-C₄)alkoxycarbonyl, (C₁-C₄)alkylcarbonylamino, acylamino,        carbamoyl or (C₁-C₄)alkylsulfonylamino group, an aminosulfonyl        radical or a radical (C₁-C₁₆)alkyl optionally substituted with a        group chosen from (C₁-C₁₂)alkoxy, hydroxyl, cyano, carboxyl,        amino and (di)(C₁-C₄)alkylamino, or alternatively the two alkyl        radicals borne by the nitrogen atom of the amino group form a 5-        to 7-membered heterocycle optionally comprising another nitrogen        or non-nitrogen heteroatom; in particular, R_(g), R′_(g),        R″_(g), R′″_(g), R_(h), R′_(h), R″_(h) and R′″_(h) represent a        hydrogen atom or a (C₁-C₄)alkyl group;    -   R′_(i), R″_(i), R′″_(i) and R″″_(i), which may be identical or        different, represent a hydrogen atom or a (C₁-C₄)alkyl group; in        particular R′_(i), R″_(i), R′″_(i), and R″″_(i) represent a        hydrogen atom;    -   m, m′, which may be identical or different, represent an integer        between 1 and 10 inclusive; in particular an integer between 2        and 4 inclusive; preferentially, m and m′ are equal to 2;    -   p, p′, q and q′, which may be identical or different, represent        an integer between 1 and 6 inclusive;    -   M′ representing an anionic counterion; and    -   Y is as defined previously;        -   it being understood that when the compound of formula (XV)            or (XV′) contains other cationic parts, it is combined with            one or more anionic counterions that afford formula (XV) or            (XV′) electrical neutrality.

According to one particular mode of the invention, the dyes of theinvention belong to formula (XVa) or (XV′a) which bear an ethylene groupconnecting the pyridinium part to the phenyl ortho or para to thepyridinium, i.e. 2-4′, 4-2′, 4-4′:

with R, R′, R″, R′″, R_(g), R′_(g), R″_(g), R′″_(g), R_(h), R′_(h),R″_(h), R′″_(h), R′_(i), R″_(i), R′″_(i), R″″_(i), m, m′, p, p′, q, q′,Y and M′ as defined previously in formulae (XV) and (XV′). Inparticular, R_(h) and R″_(h) are ortho to the pyridinium group andR′_(h) and R″_(h) represent a hydrogen atom. Another aspect of theinvention concerns the dyes of formula (XVa) or (XV′a) bearing groupsR_(g), R″_(g) in position 3′ and R′_(g)/R″_(g) which represent ahydrogen atom.

Advantageously, the dyes of formulae (XVa) and (XV′a) bear theirethylene group para to the phenyl bearing the amino group:R′(CH₂)_(p)—N—(CH₂)_(q)—R and/or R″(CH₂)_(p′)—N—(CH₂)_(q′)—R′″, i.e. inposition 4′, preferentially bear an ethylene or styryl group linking thepyridinium part to the phenyl ortho to the pyridinium, i.e. 2-4′.

According to another particular mode of the invention, the dyes of theinvention belong to formula (XVI) or (XVI′):

in which formula (XVI) or (XVI′):

-   -   R₁ represents a C₁-C₆ alkyl group substituted with one or more        hydroxyl groups or —C(O)OR′ with R′ representing a hydrogen        atom, a C₁-C₄ alkyl group or a group —C(O)—O— and, in the latter        case, an anionic counterion An⁻ is absent; in particular R₁        represents a C₁-C₆ alkyl group substituted with one or more        hydroxyl groups and more specifically with only one hydroxyl        group;    -   R₂ represents a C₁-C₆ alkyl group optionally substituted with        one or more hydroxyl groups;    -   or alternatively the groups R₁ and R₂ form, together with the        nitrogen atom that bears them, a saturated heterocyclic radical        substituted with at least one hydroxyl,        (poly)hydroxy(C₁-C₄)alkyl and/or —C(O)OR′ group with R′        representing a hydrogen atom, a C₁-C₄ alkyl group or a group        —C(O)—O⁻ and, in the latter case, an anionic counterion An⁻ is        absent; such as pyrrolidinyl and piperidyl;    -   R₃ represents a hydrogen atom or a group —C(O)OR″ with R″        representing a hydrogen atom, an alkali metal or a C₁-C₆ alkyl        group or alternatively R₃ represents a group —C(O)—O⁻ and, in        the latter case, an anionic counterion An⁻ is absent;    -   Z represents a divalent amido group —C(O)—N(R)—, —N(R)—C(O)—, or        a divalent C₁-C₁₀ alkylene group interrupted with an amido group        —C(O)—N(R)—, —N(R)—C(O)— such as        —(CH₂)_(n′)—C(O)—N(R)—(CH₂)_(p)—,        —(CH₂)_(n″)—N(R)—C(O)—(CH₂)_(p)—, with n′ representing an        integer between 0 and 3 inclusive; preferentially, n′ is equal        to 0, 2, 3; p representing an integer between 0 and 4 inclusive,        n″ representing an integer between 0 and 3 inclusive and        especially n′=n″=p=0 and R representing a hydrogen atom or a        C₁-C₆ alkyl group;    -   An⁻ represents an anionic counterion;    -   Y is as defined previously;        it being understood that when the compound of formula (XVI) or        (XVI′) contains other cationic parts, it is combined with one or        more anionic counterions that afford formula (XVI) or (XVI′)        electrical neutrality.

According to one particular mode of the invention, the dyes of theinvention belong to formula (XVIa) or (XVI′a):

in which formulae (Ia) and (Ib):

-   -   R′₁ represents a C₁-C₄ alkyl group substituted with one or more        hydroxyl groups, particularly with only one hydroxyl group, or        —C(O)OR′ with R′ representing a hydrogen atom, a C₁-C₄ alkyl        group or a group —C(O)—O— and, in the latter case, an anionic        counterion An⁻ is absent; preferentially, R′₁ represents a C₁-C₄        alkyl group substituted with a hydroxyl group;    -   R′₂ represents a C₁-C₄ alkyl group optionally substituted with        one or more hydroxyl groups, particularly with only one hydroxyl        group;    -   more particularly, R′₁ and R′₂ are identical;    -   An⁻ represents an anionic counterion as defined previously;    -   B, represent a divalent amido group —C(O)—N(R)—, —N(R)—C(O)—,        with R representing a hydrogen atom or a group (C₁-C₆)alkyl;        preferentially, R═H;    -   n and m, which may be identical or different, represent an        integer between 1 and 4 inclusive; preferentially, n is equal to        3 and m is equal to 2;    -   Y is as defined previously;        it being understood that the bond between the pyridinium ring        and the double bond of the ethylene or styryl group is located        in position 2 or 4 of the pyridinium, preferentially at 4.

As examples of disulfide, thiol and protected-thiol direct dyes offormula (I) of the invention, mention will be made of those having thefollowing chemical structures:

with An⁻ and M′, which may be identical or different, preferentiallyidentical, representing anionic counterions. More particularly, theanionic counterion is chosen from halides such as chloride, alkylsulfates such as methyl sulfate, mesylate and ½ (O═)₂SO²⁻ or ½ SO₄ ²⁻.

More preferentially, the dyes i) as defined previously are chosen fromcompounds 44, 49, 49a and 55, especially 44, 49 and 55.

According to one particularly advantageous embodiment of the invention,the dye i) is a dye comprising a “permanent” cationic charge, i.e.containing in its structure at least one quaternized nitrogen atom(ammonium) or at least one quaternized phosphorus atom (phosphonium);preferentially quaternized nitrogen.

The composition according to the invention contains, in a cosmeticmedium, an amount of dyes bearing a disulfide, thiol or protected-thiolfunction as defined previously, especially of formula (I) as definedpreviously, generally inclusively between 0.001% and 30% relative to thetotal weight of the composition.

Preferably, the amount of dyes bearing a disulfide, thiol orprotected-thiol function as defined previously, especially of formula(I), is inclusively between 0.01% and 5% by weight relative to the totalweight of the composition. By way of example, the dye(s) are in anamount of between 0.01% and 2% inclusive.

Preferably, the composition of the dyeing and/or lightening process ofthe invention is in liquid form and contains one or more cationic directdyes of formula (I) bearing a disulfide function as defined previously.

i).5). The Cosmetically Acceptable Organic or Mineral Acid Salt andCounterion of the Dyes of the Invention

They are chosen from the “organic or mineral acid salt” and “anioniccounterion” as defined previously.

Moreover, the addition salts that may be used in the context of theinvention may be chosen from addition salts with a cosmeticallyacceptable base such as basifying agents as defined below, for instancealkali metal hydroxides such as sodium hydroxide, potassium hydroxide,aqueous ammonia, amines or alkanolamines.

ii) At Least One Nonionic Surfactant;

The composition according to the invention contains ii) one or morenonionic surfactants.

Among the nonionic surfactants according to the invention, mention maybe made, alone or as mixtures, of fatty alcohols, α-diols andalkylphenols, these three types of compound being polyethoxylated,polypropoxylated and/or polyglycerolated and containing a fatty chaincomprising, for example, 8 to 40 carbon atoms, the number of ethyleneoxide or propylene oxide groups possibly ranging especially from 2 to 50and the number of glycerol groups possibly ranging especially from 2 to30. Mention may also be made of copolymers of ethylene oxide andpropylene oxide, condensates of ethylene oxide and of propylene oxidewith fatty alcohols; polyethoxylated fatty amides preferably having from2 to 30 mol of ethylene oxide, polyglycerolated fatty amides containingon average 1 to 5, and in particular 1.5 to 4 glycerol groups,ethoxylated fatty acid esters of sorbitan containing from 2 to 30 mol ofethylene oxide, fatty acid esters of sucrose, fatty acid esters ofpolyethylene glycol, alkylpolyglycosides, N-alkylglucamine derivatives,amine oxides such as (C₁₀-C₁₄)alkylamine oxides orN-acylaminopropylmorpholine oxides.

Preferably the nonionic surfactant is chosen from:

-   -   (poly)ethoxylated fatty alcohols;    -   glycerolated fatty alcohols;    -   alkylpolyglycosides.

The term “fatty chain” means a linear or branched, saturated orunsaturated hydrocarbon-based chain comprising from 6 to 30 carbon atomsand preferably from 8 to 30 carbon atoms.

As regards the alkylpolyglycosides, these compounds are well known andmay be represented more particularly by the following general formula:R₁O—(R₂O)_(t)(G)_(v)  (XVII)in which formula (XVII):

-   -   R₁ represents a linear or branched alkyl and/or alkenyl radical        comprising from about 8 to 24 carbon atoms, or an alkylphenyl        radical whose linear or branched alkyl radical comprises from 8        to 24 carbon atoms;    -   R₂ represents an alkylene radical comprising from about 2 to 4        carbon atoms;    -   G represents a sugar unit comprising from 5 to 6 carbon atoms;    -   t is an integer between 0 and 10 inclusive, preferably between 0        and 4 and in particular between 0 and 4; and    -   v denotes an integer between 1 and 15 inclusive.

Preferred alkylpolyglycosides according to the present invention arecompounds of formula (XVII) in which R₁ more particularly denotes alinear or branched, saturated or unsaturated alkyl radical comprisingfrom 8 to 18 carbon atoms, t denotes a value ranging from 0 to 3 andmore particularly equal to 0, and G may denote glucose, fructose orgalactose, preferably glucose. The degree of polymerization, i.e. thevalue of v in formula (V), may range from 1 to 15 and preferably from 1to 4. The average degree of polymerization is more particularly between1 and 2 and even more preferentially from 1.1 to 1.5.

The glycoside bonds between the sugar units are of 1-6 or 1-4 type andpreferably of 1-4 type.

Compounds of formula (XVII) are especially represented by the productssold by the company Cognis under the names Plantaren® (600 CS/U, 1200and 2000) or Plantacare® (818, 1200 and 2000). It is also possible touse the products sold by the company SEPPIC under the names Triton CG110 (or Oramix CG 110) and Triton CG 312 (or Oramix® NS 10), theproducts sold by the company BASF under the name Lutensol GD 70 or thosesold by the company Chem Y under the name AG10 LK.

It is also possible to use, for example, (C₈-C₁₆)alkyl-1,4-polyglucosideas an aqueous 53% solution, sold by the company Cognis under thereference Plantacare® 818 UP.

As regards the mono- or polyglycerolated surfactants, they preferablycomprise on average from 1 to 30 glycerol groups, more particularly from1 to 10 and in particular from 1.5 to 5 glycerol groups.

The monoglycerolated or polyglycerolated surfactants are preferablychosen from the compounds of the following formulae:RO[CH₂CH(CH₂OH)O]_(m)H,RO[CH₂CH(OH)CH₂O]_(m)H or RO[CH(CH₂OH)CH₂O]_(m)H;in which formulae:

-   -   R represents a saturated or unsaturated, linear or branched        hydrocarbon-based radical comprising from 8 to 40 carbon atoms        and preferably from 10 to 30 carbon atoms; m is an integer        between 1 and 30, preferably between 1 to 10 and more        particularly from 1.5 to 6; R may optionally comprise        heteroatoms, for instance oxygen and nitrogen. In particular, R        may optionally comprise one or more hydroxyl and/or ether and/or        amide groups. R preferably denotes optionally mono- or        polyhydroxylated C₁₀-C₂₀ alkyl and/or alkenyl radicals.

Use may be made, for example, of the polyglycerolated (3.5 mol)hydroxylauryl ether sold under the name Chimexane® NF from Chimex.

The (poly)ethoxylated fatty alcohols that are suitable for performingthe invention are chosen more particularly from alcohols containing from8 to 30 carbon atoms, and preferably from 12 to 22 carbon atoms.

The (poly)ethoxylated fatty alcohols more particularly contain one ormore linear or branched, saturated or unsaturated hydrocarbon-basedgroups, comprising 8 to 30 carbon atoms, which are optionallysubstituted, in particular with one or more (in particular 1 to 4)hydroxyl groups. If they are unsaturated, these compounds may compriseone to three conjugated or non-conjugated carbon-carbon double bonds.

The (poly)ethoxylated fatty alcohol(s) preferably have the followingformula:R^(a)—[O—CH₂—CH₂]_(n)—OH

-   -   with    -   R^(a) representing a linear or branched C₈-C₄₀ alkyl or linear        or branched C₈-C₄₀ and preferably C₈-C₃₀ alkenyl group,        optionally substituted with one or more hydroxyl groups, and    -   n is an integer between 1 and 200 inclusive, preferentially        between 2 and 50 and more particularly between 8 and 30, such as        20.

The (poly)ethoxylated fatty alcohols are more particularly fattyalcohols comprising from 8 to 22 carbon atoms, oxyethylenated with 1 to30 mol of ethylene oxide (1 to 30 OE). Among these, mention may be mademore particularly of lauryl alcohol 2 OE, lauryl alcohol 3 OE, decylalcohol 3 OE, decyl alcohol 5 OE and oleyl alcohol 20 OE.

Mixtures of these (poly)oxyethylenated fatty alcohols may also be used.

Among the nonionic surfactants, use is preferably made of C₆-C₂₄ alkylpolyglucosides and (poly)ethoxylated fatty alcohols, and C₈-C₁₆ alkylpolyglucosides are more particularly used.

The amount of nonionic surfactant preferably ranges from 0.5% to 25% byweight, in particular from 1% to 20% by weight and more particularlyfrom 2% to 10% by weight relative to the total weight of the compositionof the invention.

iii) At Least One Amphoteric Surfactant;

The composition according to the invention contains iii) one or moreamphoteric surfactants.

The amphoteric or zwitterionic surfactant(s) that may be used in thepresent invention may especially be optionally quaternized secondary ortertiary aliphatic amine derivatives containing at least one anionicgroup, for instance a carboxylate, sulfonate, sulfate, phosphate orphosphonate group, and in which the aliphatic group or at least one ofthe aliphatic groups is a linear or branched chain comprising from 8 to22 carbon atoms.

Mention may be made in particular of (C₈-C₂₀)alkylbetaines,sulfobetaines, (C₈-C₂₀ alkyl)amido(C₂-C₈ alkyl)betaines and (C₈-C₂₀alkyl)amido(C₂-C₈ alkyl)sulfobetaines.

Among the optionally quaternized secondary or tertiary aliphatic aminederivatives that may be used, as defined above, mention may also be madeof the compounds of respective structures (XVII) and (XVIII) below:R_(a)—C(O)—NH—CH₂—CH₂—N⁺(R_(b))(R_(c))—CH₂—C(O)—O⁻  (XVIII)in which formula (XVIII):

-   -   R_(a) represents a C₁₀-C₃₀ alkyl or alkenyl group derived from        an acid R_(a)—C(O)—OH preferably present in hydrolysed coconut        oil, or a heptyl, nonyl or undecyl group;    -   R_(b) represents a β-hydroxyethyl group; and    -   R_(c) represents a carboxymethyl group;        and        R_(a′)—C(O)—NH—CH₂—CH₂—N(B)B′  (XIX)        in which formula (XIX):    -   B represents —CH₂CH₂OX′;    -   B′ represents —(CH₂)_(z)—Y′, with z=1 or 2;    -   X′ represents the group —CH₂—C(O)—OH, —CH₂—C(O)—OZ′,        —CH₂CH₂—C(O)—OH, —CH₂—CH₂—C(O)—OZ′, or a hydrogen atom;    -   Y′ represents —C(O)—OH, —C(O)—OZ′ or the group —CH₂—CH(OH)—SO₃H        or —CH₂—CH(OH)—SO₃Z′;    -   Z′ represents an ion derived from an alkali or alkaline-earth        metal, such as sodium, potassium or magnesium; an ammonium ion;        or an ion derived from an organic amine and in particular from        an aminoalcohol, such as mono-, di- and triethanolamine, mono-,        di- or triisopropanolamine, 2-amino-2-methyl-1-propanol,        2-amino-2-methyl-1,3-propanediol and        tris(hydroxymethyl)aminomethane.    -   R_(a′) represents a C₁₀-C₃₀ alkyl or alkenyl group of an acid        R_(a′)C(O)—OH preferably present in coconut oil or in hydrolysed        linseed oil, an alkyl group, especially of C₁₇ and its iso form,        or an unsaturated C₁₇ group.

The compounds corresponding to formula (XIX) are preferred. Thesecompounds are also classified in the CTFA dictionary, 5th edition, 1993,under the names disodium cocoamphodiacetate, disodiumlauroamphodiacetate, disodium caprylamphodiacetate, disodiumcaprylamphodiacetate, disodium cocoamphodipropionate, disodiumlauroamphodipropionate, disodium caprylamphodipropionate, disodiumcaprylamphodipropionate, lauroamphodipropionic acid,cocoamphodipropionic acid.

By way of example, mention may be made of the N-cocoylamidocarboxymethylglycinate of an alkali metal such as sodium, or cocoamphodiacetate soldby the company Rhodia under the trade name Miranol® C2M concentrate.

Among all the amphoteric or zwitterionic surfactants iii) mentionedabove, use is preferably made of cocoylamidopropylbetaine, cocoylbetaineand the N-cocoylamidocarboxymethyl glycinate of an alkali metal such assodium.

The composition according to the invention preferably comprises from0.01% to 20% by weight, in particular from 0.5% to 10% by weight andbetter still from 1% to 5% by weight of amphoteric or zwitterionicsurfactant(s) iii), relative to the total weight of the composition.

Advantageously, the composition according to the invention may comprisea weight ratio of the amount of nonionic surfactant(s) ii) to the amountof amphoteric or zwitterionic surfactant(s) iii) of greater than 1 andbetter still greater than 3. Preferably, the weight ratio of the amountof nonionic surfactant(s) ii) to the amount of amphoteric orzwitterionic surfactant(s) iii) is less than or equal to 100, betterstill less than or equal to 50, even better still less than or equal to20 and even more preferentially less than 10.

iv) At Least One Alkaline Agent;

The composition according to the invention comprises one or morealkaline agents. This agent may be chosen from mineral or organic orhybrid alkaline agents, or mixtures thereof.

The mineral alkaline agent(s) are preferably chosen from aqueousammonia, alkali carbonates or bicarbonates such as sodium or potassiumcarbonates and sodium or potassium bicarbonates, sodium hydroxide orpotassium hydroxide, or mixtures thereof.

According to one advantageous embodiment of the invention, the alkalineagent(s) are organic amines, i.e. they contain at least one substitutedor unsubstituted amino group.

The organic alkaline agent(s) are preferably chosen from organic amineswith a pK_(b) at 25° C. of less than 12, preferably less than 10 andeven more advantageously less than 6. It should be noted that it is thepK_(b) corresponding to the function of highest basicity.

Hybrid compounds that may be mentioned include the salts of the aminesmentioned previously with acids such as carbonic acid or hydrochloricacid.

The organic alkaline agent(s) are chosen, for example, fromalkanolamines, oxyethylenated and/or oxypropylenated ethylenediamines,amino acids and the compounds of formula (XX) below:

in which formula (XX):

-   -   W is a divalent C₁-C₆ alkylene radical optionally substituted        with a hydroxyl group or a C₁-C₆ alkyl radical, and/or        optionally interrupted with one or more heteroatoms such as        oxygen or NR^(u);    -   R^(x), R^(Y), R^(z) R^(t) and R^(u), which may be identical or        different, represent a hydrogen atom or a C₁-C₆ alkyl, C₁-C₆        hydroxyalkyl or C₁-C₆ aminoalkyl radical.

Examples of such amines that may be mentioned include1,3-diaminopropane, 1,3-diamino-2-propanol, spermine and spermidine.

The term “alkanolamine” means an organic amine comprising a primary,secondary or tertiary amine function, and one or more linear or branchedC₁-C₈ alkyl groups bearing one or more hydroxyl radicals.

Alkanolamines such as monoalkanolamines, dialkanolamines ortrialkanolamines comprising from one to three identical or differentC₁-C₄ hydroxyalkyl radicals are in particular suitable for performingthe invention.

Among compounds of this type, mention may be made of monoethanolamine,diethanolamine, triethanolamine, monoisopropanolamine,diisopropanolamine, N-dimethylaminoethanolamine,2-amino-2-methyl-1-propanol, triisopropanolamine,2-amino-2-methyl-1,3-propanediol, 3-amino-1,2-propanediol,3-dimethylamino-1,2-propanediol and tris(hydroxymethylamino)methane.

More particularly, the amino acids that may be used are of natural orsynthetic origin, in their L, D or racemic form, and comprise at leastone acid function chosen more particularly from carboxylic acid,sulfonic acid, phosphonic acid or phosphoric acid functions. The aminoacids may be in neutral or ionic form.

As amino acids that may be used in the present invention, mention may bemade especially of aspartic acid, glutamic acid, alanine, arginine,ornithine, citrulline, asparagine, carnitine, cysteine, glutamine,glycine, histidine, lysine, isoleucine, leucine, methionine,N-phenylalanine, proline, serine, taurine, threonine, tryptophan,tyrosine and valine.

Advantageously, the amino acids are basic amino acids comprising anadditional amine function optionally included in a ring or in a ureidofunction.

Such basic amino acids are preferably chosen from those corresponding toformula (XXI) below:

in which formula (XX):

-   -   R denotes a group chosen from:

aminopropyl: —(CH₂)₃—NH₂, aminoethyl —(CH₂)₂—NH₂, —(CH₂)²⁻NH—C(O)—NH₂and

The compounds corresponding to formula (XXI) are histidine, lysine,arginine, ornithine and citrulline.

The organic amine may also be chosen from organic amines of heterocyclictype. Besides histidine that has already been mentioned in the aminoacids, mention may be made in particular of pyridine, piperidine,imidazole, triazole, tetrazole and benzimidazole.

The organic amine may also be chosen from amino acid dipeptides. Asamino acid dipeptides that may be used in the present invention, mentionmay be made especially of carnosine, anserine and baleine.

The organic amine is chosen from compounds comprising a guanidinefunction. As amines of this type that may be used in the presentinvention, besides arginine, which has already been mentioned as anamino acid, mention may be made especially of creatine, creatinine,1,1-dimethylguanidine, 1,1-diethylguanidine, glycocyamine, metformin,agmatine, N-amidinoalanine, 3-guanidinopropionic acid,4-guanidinobutyric acid and2-([amino(imino)methyl]amino)ethane-1-sulfonic acid.

Mention may be made in particular of the use of guanidine carbonate ormonoethanolamine hydrochloride as hybrid compounds.

The composition of the invention preferably contains one or morealkanolamines and/or one or more basic amino acids, more advantageouslyone or more alkanolamines. More preferentially still, the organic amineis monoethanolamine.

According to one particular embodiment, the composition of the inventioncomprises, as alkaline agent, one or more alkanolamines.

Preferably, the alkanolamine is ethanolamine (or monoethanolamine).

In one variant of the invention, the composition comprises, as alkalineagent, one or more alkanolamines (preferably ethanolamine) and aqueousammonia. In this variant, the alkanolamine(s) are present in apredominant amount relative to the aqueous ammonia.

Advantageously, the composition according to the invention has a contentof alkaline agent(s) ranging from 0.01% to 30% by weight, preferablyfrom 0.1% to 20% by weight and better still from 1% to 10% by weightrelative to the weight of the said composition.

v) At Least One Reducing Agent.

The composition of the invention comprises one or more reducing agents.

Preferably, the reducing agent(s) are chosen from thiols such asthioglycolic acid, thiolactic acid, 3-mercaptopropionic acid, thiomalicacid, 2,3-dimercaptosuccinic acid, cysteine, N-glycyl-L-cysteine,L-cysteinylglycine and also esters and salts thereof, thioglycerol,cysteamine and C₁-C₄ acyl derivatives thereof, N-mesylcysteamine,N-acetylcysteine, N-mercaptoalkylamides of sugars such asN-(mercapto-2-ethyl) gluconamide, pantetheine,N-(mercaptoalkyl)-ω-hydroxyalkylamides, for example those described inpatent application EP-A-354 835, N-mono- orN,N-dialkylmercapto-4-butyramides, for example those described in patentapplication EP-A-368 763, aminomercaptoalkyl amides, for example thosedescribed in patent application EP-A-432 000,N-(mercaptoalkyl)succinamic acids and N-(mercaptoalkyl)succinimides, forexample those described in patent application EP-A-465 342, alkylaminomercaptoalkyl amides, for example those described in patent applicationEP-A-514 282, the azeotropic mixture of 2-hydroxypropyl thioglycolateand of (2-hydroxy-1-methyl)ethyl thioglycolate as described in patentapplication FR-A-2 679 448, mercaptoalkylamino amides, for example thosedescribed in patent application FR-A-2 692 481, andN-mercaptoalkylalkanediamides, for example those described in patentapplication EP-A-653 202.

The reducing agent may alternatively be chosen from hydrides such assodium or potassium borohydride or alkali metal or alkaline-earth metalsulfites or bisulfites; or alternatively from phosphorus derivativessuch as phosphines or phosphites.

The reducing agent(s) are preferably chosen from thiols.

The preferred reducing agents are thioglycolic acid and cysteine, orderivatives thereof. The reducing agent is preferably used as an aqueoussolution.

In general, the concentration of reducing agent(s) is inclusivelybetween 0.01% and 30% by weight, preferably between 0.1% and 25% byweight and more particularly between 0.5% and 10% by weight relative tothe total weight of the composition applied to the keratin fibres.

vi) Optionally at Least One Oxidizing Agent

The composition according to the invention may also comprise one or morechemical oxidizing agent(s). The term “chemical oxidizing agents” meansoxidizing agents other than atmospheric oxygen.

The chemical oxidizing agents are for example chosen from hydrogenperoxide, urea peroxide, alkali metal bromates or ferricyanides,peroxygenated salts, for instance persulfates, perborates, peracids andprecursors thereof and percarbonates of alkali metals or alkaline-earthmetals. Advantageously, the oxidizing agent is hydrogen peroxide.

The content of oxidizing agent(s) more particularly represents from 0.1%to 20% by weight and preferably from 0.5% to 10% by weight relative tothe weight of the composition containing them.

vii) Optionally at Least One Thickening Organic Polymer;

The composition according to the invention may also contain vii) one ormore thickening organic polymers.

the term “thickening polymer” means a polymer which, when introduced at1% by weight in an aqueous solution or an aqueous-alcoholic solutioncontaining 30% ethanol, and at pH 7, or in an oil chosen from liquidpetroleum jelly, isopropyl myristate or cyclopentadimethylsiloxane,makes it possible to achieve a viscosity of at least 100 cps andpreferably of at least 500 cps, at 25° C. and at a shear rate of 1 s⁻¹.This viscosity may be measured using a cone/plate viscometer (Haake R600rheometer or the like). The thickening polymers may thicken the aqueousphase and/or the fatty phase, preferentially the aqueous phase.

the term “organic thickening polymer” means a thickening polymer asdefined previously, which is formed from carbon and hydrogen, andpossibly nitrogen, oxygen, sulfur, halogens such as fluorine, chlorineor bromine, and also phosphorus, alkali metals such as sodium orpotassium, or alkaline-earth metals such as magnesium or calcium. Theorganic polymers according to the invention do not comprise silicon.

The organic thickening polymers according to the invention may be ofnatural or synthetic origin.

The thickening polymers may be anionic, cationic, amphoteric or nonionicassociative or non-associative polymers.

They may be thickeners for the aqueous or oily phases.

Aqueous-phase-thickening polymers that may be mentioned includenon-associative thickening polymers bearing sugar units.

For the purposes of the present invention, the term “sugar unit” means aunit derived from a carbohydrate of formula C_(n)(H₂O)_(n-1) or(CH₂O)_(n), which may be optionally modified by substitution and/or byoxidation and/or by dehydration.

The sugar units that may be included in the composition of thethickening polymers of the invention are preferably derived from thefollowing sugars:

-   -   glucose;    -   galactose;    -   arabinose;    -   rhamnose;    -   mannose;    -   xylose;    -   fucose;    -   anhydrogalactose;    -   galacturonic acid;    -   glucuronic acid;    -   mannuronic acid;    -   galactose sulfate;    -   anhydrogalactose sulfate and    -   fructose.

Thickening polymers of the invention that may especially be mentionedinclude native gums such as:

-   -   a) tree or shrub exudates, including:        -   gum arabic (branched polymer of galactose, arabinose,            rhamnose and glucuronic acid);        -   ghatti gum (polymer derived from arabinose, galactose,            mannose, xylose and glucuronic acid);        -   karaya gum (polymer derived from galacturonic acid,            galactose, rhamnose and glucuronic acid);        -   gum tragacanth (or tragacanth) (polymer of galacturonic            acid, galactose, fucose, xylose and arabinose);    -   b) gums derived from algae, including:        -   agar (polymer derived from galactose and anhydrogalactose);        -   alginates (polymers of mannuronic acid and of glucuronic            acid);        -   carrageenans and furcellerans (polymers of galactose sulfate            and of anhydrogalactose sulfate);    -   c) gums derived from seeds or tubers, including:        -   guar gum (polymer of mannose and galactose);        -   locust bean gum (polymer of mannose and galactose);        -   fenugreek gum (polymer of mannose and galactose);        -   tamarind gum (polymer of galactose, xylose and glucose);        -   konjac gum (polymer of glucose and mannose);    -   d) microbial gums, including:        -   xanthan gum (polymer of glucose, mannose acetate,            mannose/pyruvic acid and glucuronic acid);        -   gellan gum (polymer of partially acylated glucose, rhamnose            and glucuronic acid);        -   scleroglucan gum (glucose polymer);    -   e) plant extracts, including:        -   cellulose (glucose polymer);        -   starch (glucose polymer) and        -   inulin.

These polymers may be physically or chemically modified. A physicaltreatment that may especially be mentioned is the temperature.

Chemical treatments that may be mentioned include esterification,etherification, amidation and oxidation reactions. These treatments canlead to polymers that may especially be nonionic, anionic or amphoteric.

Preferably, these chemical or physical treatments are applied to guargums, locust bean gums, starches and celluloses.

The nonionic guar gums that may be used according to the invention maybe modified with C₁-C₆ (poly)hydroxyalkyl groups.

Among the C₁-C₆ (poly)hydroxyalkyl groups that may be mentioned, forexample, are hydroxymethyl, hydroxyethyl, hydroxypropyl and hydroxybutylgroups.

These guar gums are well known in the prior art and can be prepared, forexample, by reacting the corresponding alkene oxides such as, forexample, propylene oxides, with the guar gum so as to obtain a guar gummodified with hydroxypropyl groups.

The degree of hydroxyalkylation preferably ranges from 0.4 to 1.2, andcorresponds to the number of alkylene oxide molecules consumed by thenumber of free hydroxyl functions present on the guar gum.

Such nonionic guar gums optionally modified with hydroxyalkyl groups aresold, for example, under the trade names Jaguar HP8, Jaguar HP60 andJaguar HP120 by the company Rhodia Chimie.

The botanical origin of the starch molecules used in the presentinvention may be cereals or tubers. Thus, the starches are chosen, forexample, from corn starch, rice starch, cassava starch, barley starch,potato starch, wheat starch, sorghum starch and pea starch.

The starches may be chemically or physically modified especially by oneor more of the following reactions: pregelatinization, oxidation,crosslinking, esterification, etherification, amidation, heattreatments.

Distarch phosphates or compounds rich in distarch phosphate willpreferentially be used, for instance the products sold under thereferences Prejel VA-70-T AGGL (gelatinized hydroxypropyl cassavadistarch phosphate), Prejel TK1 (gelatinized cassava distarch phosphate)and Prejel 200 (gelatinized acetyl cassava distarch phosphate) by thecompany Avebe, or Structure Zea from National Starch (gelatinized corndistarch phosphate).

According to the invention, amphoteric starches may also be used, theseamphoteric starches comprising one or more anionic groups and one ormore cationic groups. The anionic and cationic groups may be linked tothe same reactive site of the starch molecule or to different reactivesites; they are preferably linked to the same reactive site. The anionicgroups may be of carboxylic, phosphate or sulfate type, preferablycarboxylic. The cationic groups may be of primary, secondary, tertiaryor quaternary amine type.

The starch molecules may be derived from any plant source of starch,especially such as corn, potato, oat, rice, tapioca, sorghum, barley orwheat. It is also possible to use the starch hydrolysates mentionedabove. The starch is preferably derived from potato.

The non-associative thickening polymers of the invention may becellulose-based polymers not comprising any C₁₀-C₃₀ fatty chains intheir structure.

According to the invention, the term “cellulose-based polymer” means anypolysaccharide compound bearing in its structure sequences of glucoseresidues connected via β-1,4 bonds; besides unsubstituted celluloses,the cellulose derivatives may be anionic, cationic, amphoteric ornonionic;

Thus, the cellulose-based polymers of the invention may be chosen fromunsubstituted celluloses, including those in a monocrystalline form, andcellulose ethers.

Among these cellulose-based polymers, cellulose ethers, cellulose estersand cellulose ester ethers are distinguished.

Among the cellulose esters are inorganic esters of cellulose (cellulosenitrates, sulfates, phosphates, etc.), organic cellulose esters(cellulose monoacetates, triacetates, amidopropionates,acetatebutyrates, acetatepropionates and acetatetrimellitates, etc.),and mixed organic/inorganic esters of cellulose, such as celluloseacetatebutyrate sulfates and cellulose acetatepropionate sulfates. Amongthe cellulose ester ethers, mention may be made ofhydroxypropylmethylcellulose phthalates and ethylcellulose sulfates.

Among the nonionic cellulose ethers not containing a C₁₀-C₃₀ fattychain, i.e. “Non-associative”, mention may be made of(C₁-C₄)alkylcelluloses such as methylcelluloses and ethylcelluloses (forexample Ethocel Standard 100 Premium from Dow Chemical);(poly)hydroxy(C₁-C₄)alkylcelluloses such as hydroxymethylcelluloses,hydroxyethylcelluloses (for example Natrosol 250 HHR sold by Aqualon)and hydroxypropylcelluloses (for example Klucel EF from Aqualon); mixedcelluloses (poly)hydroxy(C₁-C₄)alkyl(C₁-C₄)alkylcelluloses such ashydroxypropyl methylcelluloses (for example Methocel E4M from DowChemical), hydroxyethyl methylcelluloses, hydroxyethyl ethylcelluloses(for example Bermocoll E 481 FQ from Akzo Nobel) and hydroxybutylmethylcelluloses.

Among the anionic cellulose ethers not containing a fatty chain, mentionmay be made of (poly)carboxy(C₁-C₄)alkylcelluloses, and salts thereof.Examples that may be mentioned include carboxymethyl celluloses,carboxymethyl methylcelluloses (for example Blanose 7M from the companyAqualon) and carboxymethylhydroxy ethylcelluloses, and the sodium saltsthereof.

Among the cationic cellulose ethers not containing a fatty chain,mention may be made of cationic cellulose derivatives, such ascopolymers of cellulose or the cellulose derivatives grafted with awater-soluble quaternary ammonium monomer, and disclosed in particularin U.S. Pat. No. 4,131,576, such as (poly)hydroxy(C₁-C₄)alkylcelluloses, for instance hydroxymethyl, hydroxyethyl or hydroxypropylcelluloses grafted in particular with amethacryloylethyltrimethylammonium,methacrylamidopropyltrimethylammonium or dimethyldiallylammonium salt.The commercial products corresponding to this definition are moreparticularly the products sold under the names Celquat® L 200 andCelquat® H 100 by the company National Starch.

Among the nonassociative thickening polymers not bearing sugar unitsthat may be used, mention may be made of crosslinked acrylic ormethacrylic acid homopolymers or copolymers, crosslinked2-acrylamido-2-methylpropanesulfonic acid homopolymers and crosslinkedacrylamide copolymers thereof, ammonium acrylate homopolymers, orcopolymers of ammonium acrylate and of acrylamide, alone or mixturesthereof.

A first family of nonassociative thickening polymers that is suitablefor use is represented by crosslinked acrylic acid homopolymers.

Among the homopolymers of this type, mention may be made of thosecrosslinked with an allyl alcohol ether of the sugar series, such as,for example, the products sold under the names Carbopol 980, 981, 954,2984 and 5984 by the company Noveon or the products sold under the namesSynthalen M and Synthalen K by the company 3 VSA.

The nonassociative thickening polymers may also be crosslinked(meth)acrylic acid copolymers, such as the polymer sold under the nameAqua SF1 by the company Noveon.

The nonassociative thickening polymers may be chosen from crosslinked2-acrylamido-2-methylpropanesulfonic acid homopolymers and thecrosslinked acrylamide copolymers thereof.

Among the partially or totally neutralized crosslinked copolymers of2-acrylamido-2-methylpropanesulfonic acid and of acrylamide, mention maybe made in particular of the product described in Example 1 of documentEP 503 853, and reference may be made to said document as regards thesepolymers.

The composition may similarly comprise, as nonassociative thickeningpolymers, ammonium acrylate homopolymers or copolymers of ammoniumacrylate and of acrylamide.

Among the ammonium acrylate homopolymers that may be mentioned is theproduct sold under the name Microsap PAS 5193 by the company Hoechst.Among the copolymers of ammonium acrylate and of acrylamide that may bementioned is the product sold under the name Bozepol C Nouveau or theproduct PAS 5193 sold by the company Hoechst. Reference may be madeespecially to documents FR 2 416 723, U.S. Pat. Nos. 2,798,053 and2,923,692 as regards the description and preparation of such compounds.

Among the aqueous-phase thickening polymers, mention may also be made ofthe non-cellulose-based associative polymers that are well known tothose skilled in the art and especially of nonionic, anionic, cationicor amphoteric nature.

It is recalled that “associative polymers” are polymers that arecapable, in an aqueous medium, of reversibly associating with each otheror with other molecules.

Their chemical structure more particularly comprises at least onehydrophilic region and at least one hydrophobic region.

The term “hydrophobic group” means a radical or polymer with a saturatedor unsaturated, linear or branched hydrocarbon-based chain, comprisingat least 10 carbon atoms, preferably from 10 to 30 carbon atoms, inparticular from 12 to 30 carbon atoms and more preferentially from 18 to30 carbon atoms.

Preferentially, the hydrocarbon-based group is derived from amonofunctional compound. By way of example, the hydrophobic group may bederived from a fatty alcohol such as stearyl alcohol, dodecyl alcohol ordecyl alcohol. It may also denote a hydrocarbon-based polymer, forinstance polybutadiene.

Among the associative polymers of anionic type that may be mentionedare:

-   -   (a) those comprising at least one hydrophilic unit and at least        one fatty-chain allyl ether unit, more particularly those whose        hydrophilic unit is formed by an ethylenic unsaturated anionic        monomer, more particularly a vinylcarboxylic acid and most        particularly an acrylic acid or a methacrylic acid or mixtures        thereof.

Among these anionic associative polymers, those that are particularlypreferred according to the invention are polymers formed from 20% to 60%by weight of acrylic acid and/or of methacrylic acid, from 5% to 60% byweight of lower alkyl(meth)acrylates, from 2% to 50% by weight offatty-chain allyl ether, and from 0 to 1% by weight of a crosslinkingagent which is a well-known copolymerizable unsaturated polyethylenicmonomer, for instance diallyl phthalate, allyl(meth)acrylate,divinylbenzene, (poly)ethylene glycol dimethacrylate ormethylenebisacrylamide.

Among the latter polymers, those most particularly preferred arecrosslinked terpolymers of methacrylic acid, of ethyl acrylate and ofpolyethylene glycol (10 EO) stearyl alcohol ether (Steareth-10), inparticular those sold by the company Ciba under the names Salcare SC 80®and Salcare SC 90®, which are aqueous 30% emulsions of a crosslinkedterpolymer of methacrylic acid, of ethyl acrylate and of steareth-10alkyl ether (40/50/10);

-   -   (b) polymers comprising i) at least one hydrophilic unit of        unsaturated olefinic carboxylic acid type, and ii) at least one        hydrophobic unit of the type such as a (C₁₀-C₃₀) alkyl ester of        an unsaturated carboxylic acid.

(C₁₀-C₃₀)alkyl esters of unsaturated carboxylic acids that are useful inthe invention comprise, for example, lauryl acrylate, stearyl acrylate,decyl acrylate, isodecyl acrylate and dodecyl acrylate, and thecorresponding methacrylates, lauryl methacrylate, stearyl methacrylate,decyl methacrylate, isodecyl methacrylate and dodecyl methacrylate.

Anionic polymers of this type are described and prepared, for example,according to patents U.S. Pat. No. 3,915,921 and U.S. Pat. No.4,509,949.

Among the anionic associative polymers of this type, use will be mademore particularly of those formed from 95% to 60% by weight of acrylicacid (hydrophilic unit), 4% to 40% by weight of C₁₀-C₃₀ alkyl acrylate(hydrophobic unit) and 0 to 6% by weight of crosslinking polymerizablemonomer, or alternatively those formed from 98% to 96% by weight ofacrylic acid (hydrophilic unit), 1% to 4% by weight of C₁₀-C₃₀ alkylacrylate (hydrophobic unit) and 0.1% to 0.6% by weight of crosslinkingpolymerizable monomer such as those described previously.

Among the said above polymers, those most particularly preferredaccording to the present invention are the products sold by the companyGoodrich under the trade names Pemulen TR1®, Pemulen TR2® and Carbopol1382®, and even more preferentially Pemulen TR1®, and the product soldby the company SEPPIC under the name Coatex SX®.

Mention may also be made of the acrylic acid/laurylmethacrylate/vinylpyrrolidone terpolymer sold under the name AcrylidoneLM by the company ISP.

-   -   (c) maleic anhydride/C₃₀-C₃₈ α-olefin/alkyl maleate terpolymers,        such as the product (maleic anhydride/C₃₀-C₃₈ α-olefin/isopropyl        maleate copolymer) sold under the name Performa V 1608® by the        company Newphase Technologies.    -   (d) acrylic terpolymers comprising:        -   about 20% to 70% by weight of an α,β-monoethylenically            unsaturated carboxylic acid [A],        -   about 20% to 80% by weight of an α,β-monoethylenically            unsaturated non-surfactant monomer other than [A],        -   about 0.5% to 60% by weight of a nonionic monourethane which            is the product of reaction of a monohydric surfactant with a            monoisocyanate containing monoethylenic unsaturation,    -    such as those described in patent application EP-A-0 173 109        and more particularly the terpolymer described in Example 3,        namely a methacrylic acid/methyl acrylate/behenyl alcohol        dimethyl-meta-isopropenylbenzylisocyanate ethoxylated (40 EO)        terpolymer, as an aqueous 25% dispersion.    -   (e) copolymers comprising among their monomers an        α,β-monoethylenically unsaturated carboxylic acid and an ester        of an α,β-monoethylenically unsaturated carboxylic acid and of        an oxyalkylenated fatty alcohol.

Preferentially, these compounds also comprise as monomer an ester of anα,β-monoethylenically unsaturated carboxylic acid and of a C₁-C₄alcohol.

An example of a compound of this type that may be mentioned is Aculyn22® sold by the company Röhm & Haas, which is a methacrylic acid/ethylacrylate/oxyalkylenated stearyl methacrylate terpolymer.

-   -   (f) amphiphilic polymers comprising at least one ethylenically        unsaturated monomer bearing a sulfonic group, in free or        partially or totally neutralized form and comprising at least        one hydrophobic part. These polymers may be crosslinked or        noncrosslinked. They are preferably crosslinked.

The ethylenically unsaturated monomers bearing a sulfonic group areespecially chosen from vinylsulfonic acid, styrenesulfonic acid,(meth)acrylamido(C₁-C₂₂)alkylsulfonic acids,N—(C₁-C₂₂)alkyl(meth)acrylamido(C₁-C₂₂)alkylsulfonic acids such asundecylacrylamidomethanesulfonic acid, and also partially or totallyneutralized forms thereof.

Use will more preferably be made of(meth)acrylamido(C₁-C₂₂)alkylsulfonic acids, such as, for example,acrylamidomethanesulfonic acid, acrylamidoethanesulfonic acid,acrylamidopropanesulfonic acid, 2-acrylamido-2-methylpropanesulfonicacid, methacrylamido-2-methylpropanesulfonic acid,2-acrylamido-n-butanesulfonic acid,2-acrylamido-2,4,4-trimethylpentanesulfonic acid,2-methacrylamidododecylsulfonic acid,2-acrylamido-2,6-dimethyl-3-heptanesulfonic acid, and also partially ortotally neutralized forms thereof.

2-Acrylamido-2-methylpropanesulfonic acid (AMPS), and also partially ortotally neutralized forms thereof, will more particularly be used.

The polymers of this family may be chosen especially from randomamphiphilic AMPS polymers modified by reaction with a C₆-C₂₂n-monoalkylamine or di-n-alkylamine, and such as those described inpatent application WO 00/31154. These polymers may also contain otherethylenically unsaturated hydrophilic monomers selected, for example,from (meth)acrylic acids, β-substituted alkyl derivatives thereof oresters thereof obtained with monoalcohols or mono- or polyalkyleneglycols, (meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconicacid or maleic acid, or mixtures of these compounds.

The preferred polymers of this family are chosen from amphiphiliccopolymers of AMPS and of at least one ethylenically unsaturatedhydrophobic monomer.

These same copolymers may also contain one or more ethylenicallyunsaturated monomers not comprising a fatty chain, such as (meth)acrylicacids, β-substituted alkyl derivatives thereof or esters thereofobtained with monoalcohols or mono- or polyalkylene glycols,(meth)acrylamides, vinylpyrrolidone, maleic anhydride, itaconic acid ormaleic acid, or mixtures of these compounds.

These copolymers are described especially in patent application EP-A-750899, patent U.S. Pat. No. 5,089,578 and in the following YotaroMorishima publications:

-   -   Self-assembling amphiphilic polyelectrolytes and their        nanostructures—Chinese Journal of Polymer Science Vol. 18, No.        40 (2000), 323-336;    -   Micelle formation of random copolymers of sodium        2-(acrylamido)-2-methylpropanesulfonate and a nonionic        surfactant macromonomer in water as studied by fluorescence and        dynamic light scattering—Macromolecules, 2000, Vol. 33, No. 10,        3694-3704;    -   Solution properties of micelle networks formed by nonionic        moieties covalently bound to a polyelectrolyte: salt effects on        rheological behavior—Langmuir, 2000, Vol. 16, No. 12, 5324-5332;    -   Stimuli responsive amphiphilic copolymers of sodium        2-(acrylamido)-2-methylpropanesulfonate and associative        macromonomers—Polym. Preprint, Div. Polym. Chem., 40 (2),        (1999), 220-221.

Among these polymers, mention may be made of:

-   -   copolymers, which may or may not be crosslinked and which may or        may not be neutralized, comprising from 15 to 60% by weight of        AMPS units and from 40 to 85% by weight of        (C₈-C₁₆)alkyl(meth)acrylamide units or of        (C₈-C₁₆)alkyl(meth)acrylate units, with respect to the polymer,        such as those described in application EP-A-750 899;    -   terpolymers comprising from 10 mol % to 90 mol % of acrylamide        units, from 0.1 mol % to 10 mol % of AMPS units and from 5 mol %        to 80 mol % of n-(C₆-C₁₈)alkylacrylamide units, such as those        described in patent U.S. Pat. No. 5,089,578.

Mention may also be made of copolymers of totally neutralized AMPS andof dodecyl methacrylate, and also crosslinked and non-crosslinkedcopolymers of AMPS and of n-dodecylmethacrylamide, such as thosedescribed in the Morishima articles mentioned above.

Among the cationic associative polymers that may be mentioned are:

-   -   (I) cationic associative polyurethanes;    -   (II) the compound sold by the company Noveon under the name Aqua        CC and which corresponds to the INCI name Polyacrylate-1        Crosspolymer.        Polyacrylate-1 Crosspolymer is the product of polymerization of        a monomer mixture comprising:    -   a di(C₁-C₄ alkyl)amino(C₁-C₆ alkyl)methacrylate,    -   one or more C₁-C₃₀ alkyl esters of (meth)acrylic acid,    -   a polyethoxylated C₁₀-C₃₀ alkyl methacrylate (20-25 mol of        ethylene oxide units),    -   a 30/5 polyethylene glycol/polypropylene glycol allyl ether,    -   a hydroxy(C₂-C₆ alkyl)methacrylate, and    -   an ethylene glycol dimethacrylate.    -   (III) quaternized (poly)hydroxyethylcelluloses modified with        groups comprising at least one fatty chain, such as alkyl,        arylalkyl or alkylaryl groups comprising at least 8 carbon        atoms, or mixtures thereof. The alkyl radicals borne by the        above quaternized celluloses or hydroxyethylcelluloses        preferably comprise from 8 to 30 carbon atoms. The aryl radicals        preferably denote phenyl, benzyl, naphthyl or anthryl groups.        Examples of quaternized alkylhydroxyethylcelluloses containing        C₈-C₃₀ fatty chains that may be mentioned include the products        Quatrisoft LM 200®, Quatrisoft LM-X 529-18-A®, Quatrisoft LM-X        529-18-B® (C₁₂ alkyl) and Quatrisoft LM-X 529-8® (C₁₈ alkyl)        sold by the company Aqualon, and the products Crodacel QM®,        Crodacel QL® (C₁₂ alkyl) and Crodacel QS® (C₁₈ alkyl) sold by        the company Croda, and the product Softcat SL 100® sold by the        company Aqualon.    -   (IV) cationic polyvinyllactam polymers.

Such polymers are described, for example, in patent applicationWO-00/68282.

As cationic poly(vinyllactam) polymers according to the invention,vinylpyrrolidone/dimethylaminopropylmethacrylamide/dodecyldimethylmethacrylamido-propylammoniumtosylate terpolymers,vinylpyrrolidone/dimethylaminopropylmethacrylamide/cocoyldimethylmethacrylamido-propylammoniumtosylate terpolymers,vinylpyrrolidone/dimethylaminopropylmethacrylamide/lauryldimethylmethacrylamido-propylammoniumtosylate or chloride terpolymers are used in particular.

The amphoteric associative polymers are preferably chosen from thosecomprising at least one non-cyclic cationic unit. Even moreparticularly, the ones that are preferred are those prepared from orcomprising 1 to 20 mol %, preferably 1.5 to 15 mol % and even moreparticularly 1.5 to 6 mol % of fatty-chain monomer relative to the totalnumber of moles of monomers.

Amphoteric associative polymers according to the invention are describedand prepared, for example, in patent application WO 98/44012.

Among the amphoteric associative polymers according to the invention,the ones that are preferred are acrylicacid/(meth)acrylamidopropyltrimethylammonium chloride/stearylmethacrylate terpolymers.

The associative polymers of nonionic type that may be used according tothe invention are preferably chosen from:

-   -   (a) copolymers of vinylpyrrolidone and of fatty-chain        hydrophobic monomers, of which examples that may be mentioned        include:        -   the products Antaron V216® and Ganex V216®            (vinylpyrrolidone/hexadecene copolymer) sold by the company            ISP,        -   the products Antaron V220® and Ganex V220®            (vinylpyrrolidone/eicosene copolymer) sold by the company            ISP.    -   (b) copolymers of C₁-C₆ alkyl methacrylates or acrylates and of        amphiphilic monomers comprising at least one fatty chain, such        as, for example, the oxyethylenated methyl acrylate/stearyl        acrylate copolymer sold by the company Goldschmidt under the        name Antil 208®.    -   (c) copolymers of hydrophilic methacrylates or acrylates and of        hydrophobic monomers comprising at least one fatty chain, for        instance the polyethylene glycol methacrylate/lauryl        methacrylate copolymer.    -   (d) polyurethane polyethers comprising in their chain both        hydrophilic blocks usually of polyoxyethylenated nature and        hydrophobic blocks, which may be aliphatic sequences alone        and/or cycloaliphatic and/or aromatic sequences.    -   (e) polymers with an aminoplast ether backbone containing at        least one fatty chain, such as the Pure Thix® compounds sold by        the company Sud-Chemie.    -   (f) celluloses or derivatives thereof, modified with groups        comprising at least one fatty chain, such as alkyl, arylalkyl or        alkylaryl groups or mixtures thereof in which the alkyl groups        are of C₈, and in particular:        -   nonionic alkylhydroxyethylcelluloses such as the products            Natrosol Plus Grade 330 CS and Polysurf 67 (C₁₆ alkyl) sold            by the company Aqualon;        -   nonionic nonoxynylhydroxyethylcelluloses such as the product            Amercell HM-1500 sold by the company Amerchol;        -   nonionic alkylcelluloses such as the product Bermocoll EHM            100 sold by the company Berol Nobel;    -   (g) associative guar derivatives, for instance hydroxypropyl        guars modified with a fatty chain, such as the product Esaflor        HM 22 (modified with a C₂₂ alkyl chain) sold by the company        Lamberti; the product Miracare XC 95-3 (modified with a C₁₄        alkyl chain) and the product RE 205-146 (modified with a C₂₀        alkyl chain) sold by Rhodia Chimie.

Preferably, the polyurethane polyethers comprise at least twohydrocarbon-based lipophilic chains containing from 6 to 30 carbonatoms, separated by a hydrophilic block, the hydrocarbon-based chainspossibly being pendent chains or chains at the end of the hydrophilicblock. In particular, it is possible for one or more pendent chains tobe included. In addition, the polymer may comprise a hydrocarbon-basedchain at one end or at both ends of a hydrophilic block.

The polyurethane polyethers may be multiblock, in particular in triblockform. The hydrophobic blocks may be at each end of the chain (forexample: triblock copolymer containing a hydrophilic central block) ordistributed both at the ends and in the chain (for example multiblockcopolymer). These same polymers may also be graft polymers or starpolymers.

The nonionic fatty-chain polyurethane polyethers may be triblockcopolymers in which the hydrophilic block is a polyoxyethylenated chaincomprising from 50 to 1000 oxyethylene groups. The nonionic polyurethanepolyethers comprise a urethane bond between the hydrophilic blocks,whence arises the name.

By extension, also included among the nonionic fatty-chain polyurethanepolyethers are those in which the hydrophilic blocks are linked to thelipophilic blocks via other chemical bonds.

As examples of nonionic fatty-chain polyurethane polyethers that may beused in the invention, it is also possible to use Rheolate 205®containing a urea function, sold by the company Rheox, or Rheolate® 208,204 or 212, and also Acrysol RM 184®.

Mention may also be made of the product Elfacos T210® containing aC₁₂₋₁₄ alkyl chain, and the product Elfacos T212® containing a C₁₈ alkylchain, from Akzo.

The product DW 1206B® from Röhm & Haas containing a C₂₀ alkyl chain anda urethane bond, sold at a solids content of 20% in water, may also beused.

It is also possible to use solutions or dispersions of these polymers,especially in water or in aqueous-alcoholic medium. Examples of suchpolymers that may be mentioned are Rheolate® 255, Rheolate® 278 andRheolate® 244 sold by the company Rheox. The products DW 1206F and DW1206J sold by the company Röhm & Haas may also be used.

The polyurethane polyethers that may be used according to the inventionare in particular those described in the article by G. Formum, J. Bakkeand Fk. Hansen—Colloid Polym. Sci. 271, 380.389 (1993).

It is even more particularly preferred to use a polyurethane polyetherthat may be obtained by polycondensation of at least three compoundscomprising (i) at least one polyethylene glycol comprising from 150 to180 mol of ethylene oxide, (ii) stearyl alcohol or decyl alcohol, and(iii) at least one diisocyanate.

Such polyurethane polyethers are sold especially by the company Röhm &Haas under the names Aculyn 46® and Aculyn 44® [Aculyn 46® is apolycondensate of polyethylene glycol containing 150 or 180 mol ofethylene oxide, of stearyl alcohol and of methylenebis(4-cyclohexylisocyanate) (SMDI), at 15% by weight in a matrix of maltodextrin (4%)and water (81%); Aculyn 44® is a polycondensate of polyethylene glycolcontaining 150 or 180 mol of ethylene oxide, of decyl alcohol and ofmethylenebis(4-cyclohexyl isocyanate) (SMDI), at 35% by weight in amixture of propylene glycol (39%) and water (26%)].

Use may also be made of fatty-phase-thickening polymers.

Preferably, the polymers for structuring the oily phase via physicalinteractions are chosen from polyamides, silicone polyamides, saccharideor polysaccharide mono- or polyalkyl esters, N-acylamino acid amidederivatives, and copolymers comprising an alkylene or styrene block,these copolymers possibly being diblock, triblock, multiblock orradial-block polymers, also known as star copolymers, or alternativelycomb polymers.

1) Polymers Bearing at Least One Crystallizable Block in the Backbone

These are also polymers that are soluble or dispersible in the oil oroily phase by heating above their melting point m.p. These polymers areespecially block copolymers consisting of at least two blocks ofdifferent chemical nature, one of which is crystallizable.

As polymers bearing in the backbone at least one crystallizable blockthat are suitable for use in the invention, mention may be made of:

i). the polymers defined in document U.S. Pat. No. 5,156,911;

ii). block copolymers of olefin or of cycloolefin containing acrystallizable chain, for instance those derived from the blockpolymerization of:

-   -   cyclobutene, cyclohexene, cyclooctene, norbornene (i.e.        bicyclo(2,2,1)-2-heptene), 5-methylnorbornene,        5-ethylnorbornene, 5,6-dimethyl-norbornene,        5,5,6-trimethylnorbornene, 5-ethylidenenorbornene,        5-phenylnorbornene, 5-benzylnorbornene, 5-vinylnorbornene,        1,4,5,8-dimethano-1,2,3,4,4a,5,8a-octahydronaphthalene,        dicyclopentadiene, and mixtures thereof,    -   with ethylene, propylene, 1-butene, 3-methyl-1-butene, 1-hexene,        4-methyl-1-pentene, 1-octene, 1-decene or 1-eicosene, or        mixtures thereof. These block copolymers may be in particular        (ethylene/norbornene) block copolymers and        (ethylene/propylene/ethylidenenorbornene) block terpolymers.

Those resulting from the block copolymerization of at least two C₂-C₁₆,and better still C₂-C₁₂, α-olefins such as those mentioned above and inparticular block bipolymers of ethylene and of 1-octene may also beused.

Copolymers containing at least one crystallizable block, the rest of thecopolymer being amorphous (at room temperature). These copolymers mayalso contain two crystallizable blocks of different chemical nature. Thepreferred copolymers are those that simultaneously contain at roomtemperature a crystallizable block and an amorphous block that are bothhydrophobic and lipophilic, sequentially distributed; mention may bemade, for example, of polymers containing one of the crystallizableblocks and one of the amorphous blocks below:

-   -   Block that is crystallizable by nature: a) of polyester type,        for instance poly(alkylene terephthalate), b) of polyolefin        type, for instance polyethylenes or polypropylenes.    -   Amorphous and lipophilic block, for instance: amorphous        polyolefins or copoly(olefin)s such as poly(isobutylene),        hydrogenated polybutadiene or hydrogenated poly(isoprene).

As examples of such copolymers containing a crystallizable block and anamorphous block, mention may be made of:

a) poly(δ-caprolactone)-b-poly(butadiene) block copolymers, preferablyused hydrogenated, such as those described in the article Meltingbehaviour of poly(δ-caprolactone)-block-polybutadiene copolymers from S,Nojima, Macromolecules, 32, 3727-3734 (1999),

b) the hydrogenated block or multiblock poly(butyleneterephthalate)-b-poly(isoprene) block copolymers cited in the articleStudy of morphological and mechanical properties of PP/PBT by B.Boutevin et al., Polymer Bulletin, 34, 117-123 (1995),

c) the poly(ethylene)-b-copoly(ethylene/propylene) block copolymerscited in the articles Morphology of semi-crystalline block copolymers ofethylene-(ethylene-alt-propylene) by P. Rangarajan et al.,Macromolecules, 26, 4640-4645 (1993) and Polymer aggregates withcrystalline cores: the system poly(ethylene)poly(ethylene-propylene) P.Richter et al., Macromolecules, 30, 1053-1068 25 (1997),

d) the poly(ethylene)-b-poly(ethylethylene) block copolymers mentionedin the general article Crystallization in block copolymers by I.W.Hamley, Advances in Polymer Science, vol. 148, 113-137 (1999).

The semi-crystalline polymers that may be used in the context of theinvention may be non-crosslinked or partially crosslinked, provided thatthe degree of crosslinking does not impede their dissolution ordispersion in the liquid oily phase by heating above their meltingpoint. It may then be a case of chemical crosslinking, by reaction witha multifunctional monomer during the polymerization. It may also be acase of physical crosslinking, which may then be due either to theestablishment of bonds of hydrogen or dipolar type between groups borneby the polymer, for instance dipolar interactions between carboxylateionomers, these interactions being in small amount and borne by thepolymer backbone; or due to a phase separation between thecrystallizable blocks and the amorphous blocks borne by the polymer.

Preferably, the semi-crystalline polymers that are suitable for theinvention are non-crosslinked.

As particular examples of semi-crystalline polymers that may be used inthe composition according to the invention, mention may be made of theIntelimer® products from the company Landec described in the brochure“Intelimer® polymers”. These polymers are in solid form at roomtemperature (25° C.). They bear crystallizable side chains and containthe monomer. Mention may be made especially of “Landec IP22®”, with amelting point m.p. of 56° C., which is a viscous, impermeable, non-tackyproduct at room temperature.

It is also possible to use the semi-crystalline polymers described inExamples 3, 4, 5, 7 and 9 of document U.S. Pat. No. 5,156,911, resultingfrom the copolymerization of acrylic acid and of C₅ to C₁₆alkyl(meth)acrylate, such as those resulting from the copolymerization:

-   -   of acrylic acid, of hexadecyl acrylate and of isodecyl acrylate        in a 1/16/3 ratio,    -   of acrylic acid and of pentadecyl acrylate in a 1/19 ratio,    -   of acrylic acid, of hexadecyl acrylate and of ethyl acrylate in        a 2.5/76.5/20 ratio,    -   of acrylic acid, of hexadecyl acrylate and of methyl acrylate in        a 5/85/10 ratio,    -   of acrylic acid and of octadecyl methacrylate in a 2.5/97.5        ratio.

It is also possible to use the polymer “Structure O” sold by the companyNational Starch, such as the product described in document U.S. Pat. No.5,736,125, of m.p. 44° C., and also semi-crystalline polymers containingcrystallizable pendent chains comprising fluoro groups as described inExamples 1, 4, 6, 7 and 8 of document WO-A-01/19333.

It is also possible to use the semi-crystalline polymers obtained bycopolymerization of stearyl acrylate and of acrylic acid or of NVP, orby copolymerization of behenyl acrylate and of acrylic acid or NVP, asdescribed in document U.S. Pat. No. 5,519,063 or EP-A-0 550 745.

According to one particular embodiment variant, the semi-crystallinepolymers that are suitable for use in the present invention areespecially alkyl acrylates, among which mention may be made of theLandec copolymers:

-   -   Doresco IPA 13-1®: polystearyl acrylate, m.p. of 49° C. and MW        of 145 000;    -   Doresco IPA 13-3®: polyacrylate/methacrylic acid, m.p. of 65° C.        and MW of 114 000;    -   Doresco IPA 13-4®: polyacrylate/vinylpyrrolidone, m.p. of 44° C.        and MW of 387 000;    -   Doresco IPA 13-5®: polyacrylate/hydroxyethyl methacrylate, m.p.        of 47° C. and MW of 397 600;    -   Doresco IPA 13-6®: polybehenyl acrylate, m.p. of 66° C.

2) Non-Silicone Polyamides

The particular polyamides used in the composition according to thepresent invention are preferably those described in document U.S. Pat.No. 5,783,657 from the company Union Camp.

Each of these polyamides especially satisfies formula (XXII) below:

in which formula (XXII):

-   -   n denotes a whole number of amide units such that the number of        ester groups represents from 10% to 50% of the total number of        ester and amide groups;    -   R₁ is independently in each case an alkyl or alkenyl group        containing at least 4 carbon atoms and especially from 4 to 24        carbon atoms;    -   R₂ represents independently in each case a C₄ to C₅₅        hydrocarbon-based group, on condition that at least 50% of the        groups R₂ represent a C₃₀ to C₅₅ hydrocarbon-based group;    -   R₃ represents independently in each case an organic group        bearing at least two carbon atoms, hydrogen atoms and optionally        one or more oxygen or nitrogen atoms; and    -   R₄ represents independently in each case a hydrogen atom, a C₁        to C₁₀ alkyl group or a direct bond to R₃ or to another R₄ such        that the nitrogen atom to which are attached both R₃ and R₄        forms part of a heterocyclic structure defined by R₄—N—R₃, with        at least 50% of the groups R₄ representing a hydrogen atom.

In particular, the ester groups of this polyamide represent from 15% to40% and at best from 20% to 35% of the total number of ester and amidegroups. Furthermore, n advantageously represents an integer ranging from1 to 10 and better still from 1 to 5, limits inclusive.

Preferably, R¹ is a C₁₂ to C₂₂ and preferably C₁₆ to C₂₂ alkyl group.Advantageously, R² may be a C₁₀ to C₄₂ hydrocarbon-based (alkylene)group. Preferably, at least 50% and better still at least 75% of thegroups R² are groups containing from 30 to 42 carbon atoms. The othergroups R² are C₄ to C₁₉ and better still C₄ to C₁₂ hydrogen-containinggroups. Preferably, R³ represents a C₂ to C₃₆ hydrocarbon-based group ora polyoxyalkylene group and R⁴ represents a hydrogen atom. Preferably,R³ represents a C₂ to C₁₂ hydrocarbon-based group. The hydrocarbon-basedgroups may be linear, cyclic or branched, and saturated or unsaturatedgroups. Moreover, the alkyl and alkylene groups may be linear orbranched, and saturated or unsaturated groups.

The thickening of the liquid oily phase may be obtained by means of oneor more polyamides defined above. In general, these polyamides are inthe form of mixtures, these mixtures also possibly containing asynthetic product corresponding to a polyamide as defined above with nbeing 0, i.e. a diester.

As structuring polyamides that may be used in the invention, mention mayalso be made of polyamide resins resulting from the condensation of analiphatic dicarboxylic acid and a diamine (including compoundscontaining, respectively, more than two carboxyl groups and more thantwo amine groups), the carbonyl and amine groups of adjacent individualunits being condensed in the form of an amide bond. These polyamideresins are especially the products sold under the brand name Versamid®by the companies General Mills, Inc. and Henkel Corp., under the brandname Onamid®, especially Onamid S or C. These resins have aweight-average molecular mass ranging from 6000 to 9000. For furtherinformation regarding these polyamides, reference may be made to U.S.Pat. Nos. 3,645,705 and 3,148,125. Use is made more especially ofVersamid® 30 or 744.

It is also possible to use the polyamides sold or manufactured by thecompany Arizona under the references Uni-Rez (2658, 2931, 2970, 2621,2613, 2624, 2665, 1554, 2623, 2662) and the product sold under thereference Macromelt 6212 by the company Henkel. For further informationregarding these polyamides, reference may be made to document U.S. Pat.No. 5,500,209.

As examples of structuring polyamides that may be used in thecomposition according to the invention, mention may also be made of thecommercial products sold or manufactured by the company Arizona Chemicalunder the names Uniclear 80 and Uniclear 100. They are sold,respectively, in the form of an 80% (active material) gel and a 100%(active material) gel in a mineral oil. They have a softening point offrom 88 to 105° C. These commercial products are a mixture of copolymersof a C36 diacid coupled with ethylenediamine, having an averagemolecular mass of about 6000. The terminal ester groups result from theesterification of the remaining acid end groups with cetyl alcohol,stearyl alcohol or mixtures thereof (also known as cetylstearylalcohol).

2) Saccharide or Polysaccharide Mono- or Polyalkyl Esters

Among the saccharide or polysaccharide monoalkyl or polyalkyl estersthat are suitable for use in the invention, mention may be made ofdextrin or inulin alkyl or polyalkyl esters.

It may especially be a dextrin mono- or polyester of at least one fattyacid corresponding especially to formula (XXIII) below:

in which formula (XXIII):

-   -   n is an integer ranging from 3 to 200, especially ranging from        20 to 150 and in particular ranging from 25 to 50,    -   R₁, R₂ and R₃, which may be identical or different, are chosen        from hydrogen and an acyl group (R—C(O)—) in which the radical R        is a linear or branched, saturated or unsaturated        hydrocarbon-based group containing from 7 to 29, in particular        from 7 to 21, especially from 11 to 19, more particularly from        13 to 17, or even 15, carbon atoms, with the proviso that at        least one of the said radicals R₁, R₂ or R₃ is other than        hydrogen.

In particular, R₁, R₂ and R₃ may represent hydrogen or an acyl group(R—C(O)—) in which R is a hydrocarbon-based radical as defined above,with the proviso that at least two of the said radicals R₁, R₂ and R₃are identical and other than hydrogen.

The radicals R₁, R₂ and R₃ may all contain an acyl group (R—C(O)), whichis identical or different and especially identical.

In particular, n mentioned above advantageously ranges from 25 to 50 andis especially equal to 38 in the general formula of the saccharide esterthat may be used in the present invention.

When the radicals R₁, R₂ and/or R₃, which may be identical or different,contain an acyl group (R—C(O)), these radicals may be chosen especiallyfrom caprylic, capric, lauric, myristic, palmitic, stearic, arachic,behenic, isobutyric, isovaleric, 2-ethylbutyric, ethylmethylacetic,isoheptanoic, 2-ethylhexanoic, isononanoic, isodecanoic, isotridecanoic,isomyristic, isopalmitic, isostearic, isoarachic, isohexanoic, decenoic,dodecenoic, tetradecenoic, myristoleic, hexadecenoic, palmitoleic,oleic, elaidic, asclepinic, gondoleic, eicosenoic, sorbic, linoleic,linolenic, punicic, stearidonic, arachidonic and stearolic radicals, andmixtures thereof.

Preferably, at least one dextrin palmitate is used as fatty acid esterof dextrin. This ester may be used alone or as a mixture with otheresters.

Advantageously, the fatty acid ester of dextrin has a degree ofsubstitution of less than or equal to 2.5, especially ranging from 1.5to 2.5 and preferably from 2 to 2.5 on the basis of one glucose unit.The weight-average molecular weight of the dextrin ester may inparticular be from 10 000 to 150 000, especially from 12 000 to 100 000and even from 15 000 to 80 000.

Dextrin esters, in particular dextrin palmitates, are commerciallyavailable under the name Rheopearl TL or Rheopearl KL by the companyChiba Flour.

3) N-Acylamino Acid Amide Derivatives

The N-acylamino acid amides that may be used are, for example, diamidesfrom the combination of an N-acylamino acid with amines comprising from1 to 22 carbon atoms, such as those described in document FR 2 281 162.They are, for example, alkylglutamic acid amide derivatives such as thelaurylglutamic acid dibutylamide sold by the company Ajinomoto under thename Gelling Agent GP-1, or alternatively the 2-ethylhexylglutamic aciddibutylamide sold by the company Ajinomoto under the name Gelling AgentGA-01.

4) Copolymers Comprising an Alkylene or Styrene Block

The copolymers may have a comb or the block structure of diblock,triblock, multiblock and/or radial or star type and may comprise atleast two thermodynamically incompatible segments.

The structuring agent may comprise, for example, a styrene segment asdescribed in patent applications EP 0 497 144, WO 98/42298, U.S. Pat.Nos. 6,225,690, 6,174,968 and 6,225,390, an ethylene/butylene segment oran ethylene/propylene segment as described in patent applications U.S.Pat. Nos. 6,225,690, 6,174,968 and 6,225,390, a butadiene segment, anisoprene segment, a polyvinyl segment, for instancepolyalkyl(meth)acrylate or polyvinyl alcohol or polyvinyl acetate, asilicone segment as described in patent applications U.S. Pat. Nos.5,468,477 and 5,725,882, or a combination of these segments.

A diblock copolymer is usually defined as being of A-B type in which ahard segment (A) is followed by a soft segment (B).

A triblock copolymer is usually defined as being of A-B-A type or as aratio of a hard segment, a soft segment and a hard segment.

A multiblock, radial or star copolymer may comprise any type ofcombination of hard segments and soft segments, with the proviso thatthe characteristics of the hard segments and of the soft segments areconserved.

An example of hard segments of block copolymers that may be mentioned isstyrene, and examples of soft segments of block copolymers that may bementioned include ethylene, propylene and butylene, and a combinationthereof.

The triblock copolymers, and especially those ofpolystyrene/polyisoprene or polystyrene/polybutadiene type, which aresuitable for use in the invention may be those sold under the referenceLuvitol HSB by the company BASF. Mention may also be made of triblockcopolymers of polystyrene/copoly(ethylene-propylene) orpolystyrene/copoly(ethylene-butylene) type, such as those sold under thereference Kraton by the company Shell Chemical Co., or under thereference Gelled Permethyl 99 A by the company Penreco. Such triblockcopolymers are particularly preferred according to the invention.

As a further example of block copolymers that may be suitable for use inthe present invention, mention may also be made of the block copolymerssold under the reference Versagel by the company Penreco, those soldunder the reference Kraton by the company Shell and those sold under thereference Gel Base by the company Brooks Industries.

Among the fatty-phase thickening polymers, polymers bearing in thebackbone at least one crystallizable block are preferred.

The aqueous-phase or fatty-phase thickening polymers may be used aloneor as mixtures in all proportions.

Preferably, the thickeners are aqueous-phase thickeners.

Preferably, the polymers in the cosmetic compositions in accordance withthe present invention advantageously have in solution or in dispersion,at 1% active material in water, a viscosity, measured using a Rheomat RM180 rheometer at 25° C., of greater than 0.1 ps and even moreadvantageously greater than 0.2 cp, at a shear rate of 200 s⁻¹.

According to one particular embodiment of the invention, the organicthickening polymer(s) are chosen from cellulose-based polymers.

The organic thickening polymer(s) may be present in the compositionaccording to the invention in a content ranging from 0.01% to 10% byweight and preferably from 0.1% to 5% by weight relative to the totalweight of the composition.

viii) Adjuvants:

The composition comprising the ingredients i) to v) as definedpreviously may also contain various adjuvants conventionally used inhair dye compositions, such as anionic, cationic or nonionicsurfactants, or mixtures thereof, anionic, cationic, nonionic,amphoteric or zwitterionic polymers or mixtures thereof, mineral ororganic thickeners, penetrants, sequestrants, fragrances, buffers,dispersants, conditioning agents, for instance volatile or non-volatile,modified or unmodified silicones, film-forming agents, ceramides,preserving agents and opacifiers.

The above adjuvants are generally present in an amount, for each ofthem, of between 0.01% and 20% by weight relative to the weight of thecomposition.

Needless to say, a person skilled in the art will take care to selectthis or these optional additional compound(s) such that the advantageousproperties intrinsically associated with the dye composition inaccordance with the invention are not, or are not substantially,adversely affected by the envisaged addition(s).

ix) Additional Dyes:

The composition comprising the dye(s) bearing a disulfide, thiol orprotected-thiol function especially of formula (I) as defined previouslyof the process of the invention may also contain one or more additionaldirect dyes other than the disulfide, thiol or protected-thiol directdyes of formula (I) according to the invention. These direct dyes arechosen, for example, from those conventionally used in direct dyeing,and among which mention may be made of any commonly used aromatic and/ornon-aromatic dye such as neutral, acidic or cationic nitrobenzene directdyes, neutral, acidic or cationic azo direct dyes, natural direct dyes,neutral, acidic or cationic quinone and in particular anthraquinonedirect dyes, azine, triarylmethane, indoamine, methine, styryl,porphyrin, metalloporphyrin, phthalocyanine, cyanine and methine directdyes, and fluorescent dyes, other than the dyes of formula (I).

Among the natural direct dyes, mention may be made of lawsone, juglone,alizarin, purpurin, carminic acid, kermesic acid, purpurogallin,protocatechaldehyde, indigo, isatin, curcumin, spinulosin, apigenidinand orceins. Extracts or decoctions containing these natural dyes and inparticular henna-based poultices or extracts, may also be used.

According to the invention, the additional direct dye(s) used accordingto the invention preferably represent from 0.001% to 10% by weightapproximately relative to the total weight of the dye compositioncomprising the dye(s) bearing a disulfide, thiol or protected-thiolfunction especially of formula (I) as defined previously and even morepreferentially from 0.05% to 5% by weight approximately.

The composition comprising the dye(s) bearing a disulfide, thiol orprotected thiol function especially of formula (I) as defined previouslyof the process of the invention may also contain one or more oxidationbases and/or one or more couplers conventionally used for the dyeing ofkeratin fibres.

Among the oxidation bases, mention may be made ofpara-phenylenediamines, bis(phenyl)alkylenediamines, para-aminophenols,bis-para-aminophenols, ortho-aminophenols and heterocyclic bases, andthe addition salts thereof.

Among these couplers, mention may be made especially ofmeta-phenylenediamines, meta-aminophenols, meta-diphenols,naphthalene-based couplers and heterocyclic couplers, and the additionsalts thereof.

The coupler(s) are each generally present in an amount of between 0.001%and 10% by weight and preferably between 0.005% and 6% by weightrelative to the total weight of the dye composition.

The oxidation base(s) present in the dye composition are each generallypresent in an amount of between 0.001% and 10% by weight and preferablybetween 0.005% and 6% by weight relative to the total weight of the dyecomposition.

In general, the addition salts of the oxidation bases and couplers usedin the context of the invention are especially chosen from the salts ofaddition with an acid, such as the hydrochlorides, hydrobromides,sulfates, citrates, succinates, tartrates, lactates, tosylates,benzenesulfonates, phosphates and acetates, and the salts of additionwith a base, such as alkali metal hydroxides, for instance sodiumhydroxide, potassium hydroxide, aqueous ammonia, amines oralkanolamines.

According to one particular embodiment, the composition of the processof the invention contains at least one oxidation base and optionally atleast one coupler as defined above.

The process of the invention may also use another composition thatcomprises one or more chemical oxidizing agents. The term “chemicaloxidizing agent” means chemical oxidizing agents other than atmosphericoxygen, such as those described previously.

The use of hydrogen peroxide is particularly preferred.

The content of oxidizing agent(s) is generally inclusively between 1%and 40% by weight relative to the weight of the composition andpreferably between 1% and 20% by weight relative to the weight of thecomposition containing them.

The pH:

The pH of the composition according to the invention is generallybetween 2 and 12 approximately and preferably between 3 and 11approximately. It may be adjusted to the desired value by means ofacidifying or basifying agents usually used in the dyeing of keratinfibres, or alternatively using standard buffer systems.

The pH of the composition is preferentially inclusively between 6 and 9,particularly between 7 and 9, and more particularly between 7.5 and 9.

Among the acidifying agents that may be mentioned, for example, aremineral or organic acids, for instance hydrochloric acid,orthophosphoric acid or sulfuric acid, carboxylic acids, for instanceacetic acid, tartaric acid, citric acid and lactic acid, and sulfonicacids.

Among the alkaline agents that may be mentioned, for example, areaqueous ammonia, alkali metal carbonates, alkanolamines such asmonoethanolamine, diethanolamine and triethanolamine, and other alkalineagents iv) as defined previously.

Forms of the Composition:

The dye composition comprising i) the dye(s) bearing a disulfide, thiolor protected-thiol function especially of formula (I) as definedpreviously and the ingredients ii), iii), iv) and v) as definedpreviously may be in various galenical forms, such as in the form ofliquids, lotions, creams or gels, or in any other form that is suitablefor dyeing keratin fibres. They may also be conditioned under pressurein an aerosol can in the presence of a propellant or in a non-aerosolcan, and form a mousse.

2). Dyeing Processes of the Invention

The process for dyeing keratin fibres, especially dark keratin fibres,according to the invention comprises the step of applying to the keratinfibres:

-   -   i) at least one cationic direct dye bearing a disulfide        function, a thiol function or a protected-thiol function as        defined previously;    -   ii) at least one nonionic surfactant;    -   iii) at least one amphoteric surfactant;    -   iv) at least one alkaline agent as defined previously;    -   v) at least one reducing agent as defined previously; and    -   vii) optionally at least one organic thickening polymer as        defined previously;        the ingredients i) to v) and optionally vii) possibly being        applied either together onto the said fibres or separately.

When it is desired to lighten dark keratin fibres without the use of achemical oxidizing agent, an ingredient i) that is fluorescent is usedin the dye composition or the dyeing process. Preferentially, thefluorescent dyes of formula (I) are chosen from the dyes of formulae(XIII), (XIII′), (XIV), (XIV′), (XVa), (XV′a), (XV) to (XV′), (XVI),(XVI′), (XVIa) and (XVI′a) as defined previously. More particularly, thefluorescent dyes i) as defined previously used for lightening keratinfibres are chosen from compounds 44, 49, 49a and 55.

The dyeing process according to the invention may be performed in onestep by applying to the keratin fibres the composition according to theinvention comprising the ingredients i) to v) and optionally vii) asdefined previously, in one or more steps.

According to one particular embodiment of the process of the invention,the reducing agent v) as defined previously may be applied as apretreatment before the application of the dye composition containingthe ingredients i) to iv) and optionally vii) as defined previously.

According to another interesting variant, the reducing compositioncomprising the reducing agent v) and the ingredients iv) and iii) asdefined previously is applied to the keratin fibres as a pretreatmentbefore the application of the dye composition comprising the ingredientsi) and ii) and optionally vii) as defined previously.

According to another variant of the invention, the reducing compositioncomprising the reducing agent v) and the ingredient iv) and optionallyvii) as defined previously is applied to the keratin fibres as apretreatment before the application of the dye composition comprisingthe ingredients i), ii) and iii) as defined previously.

According to another variant of the invention, the reducing compositioncomprising the reducing agent v) and the ingredient iii) as definedpreviously is applied to the keratin fibres as a pretreatment before theapplication of the dye composition comprising the ingredients i), ii)and iv) and optionally vii) as defined previously.

According to another variant of the invention, the reducing compositioncomprising the reducing agent v) and the ingredient ii) as definedpreviously is applied to the keratin fibres as a pretreatment before theapplication of the dye composition comprising the ingredients i), iii)and iv) and optionally vii) as defined previously.

The reducing pretreatment may be of short duration, especially from 1second to 30 minutes and preferably from 1 minute to 15 minutes, withone or more reducing agents as mentioned previously.

Between the reducing pretreatment step and the dyeing step using thecomposition comprising the ingredient i) as defined previously, thekeratin fibres are preferentially rinsed with water.

The leave-on time of the dye composition, i.e. comprising the ingredienti) as defined previously, is inclusively between 5 minutes and 1 hourand preferably between 10 minutes and 40 minutes.

The dye composition, i.e. the composition comprising the ingredient i),is generally applied at room temperature. However, it may be applied attemperatures ranging from 20 to 180° C.

According to another variant, instead of using the reducing agent as apretreatment, it is used as a post-treatment, after the application ofthe dye composition.

According to another particular dyeing process of the invention, thedyeing process does not comprise any reducing pretreatment orpost-treatment step. In this case, the dyeing process comprises the stepof applying the composition according to the invention, which comprisesthe ingredients i) to v) and optionally vii) as defined previously.

When the ingredient i) is a protected-thiol dye, i.e. the thiol dye offormula (I) as defined previously in which U=Y with Y being a protectinggroup, the process of the invention may be preceded by a deprotectionstep for restoring the SH function in situ.

By way of example, it is possible to deprotect the function S—Y of thedyes of the invention with Y being a protecting group, by adjusting thepH as follows:

Y: protecting group deprotection alkylcarbonyl, pH > 9 arylcarbonyl,pH > 9 alkoxycarbonyl, pH > 9 aryloxycarbonyl, pH > 9arylalkoxycarbonyl, pH > 9 (di)(alkyl)aminocarbonyl, pH > 9(alkyl)arylaminocarbonyl, pH > 9 optionally substituted aryl such asphenyl, pH > 9 5-, 6- or 7-membered monocyclic heteroaryl pH > 9 such asoxazolium, 8- to 11-membered bicyclic heteroaryl such as pH > 9benzimidazolium or benzoxazolium

The deprotection step may also be performed during a step ofpretreatment of the hair, for instance the hair reducing pretreatment.

A treatment with one or more chemical oxidizing agents may optionally beperformed after the application of ingredients i) to v) and optionallyvii) as defined previously to the keratin fibres. To do this, a fixingcomposition comprising a cosmetic chemical oxidizing agent such as theingredient vi) defined previously may be used. Thus, it may be chosenespecially from hydrogen peroxide, urea peroxide, alkali metal bromates,persalts such as perborates and persulfates, and also enzymes, amongwhich mention may be made of peroxidases, 2-electron oxidoreductasessuch as uricases, and 4-electron oxygenases such as laccases. The use ofhydrogen peroxide is particularly preferred.

The leave-on time of the oxidizing (fixing) composition is inclusivelybetween 1 second and 40 minutes and preferably between 15 seconds and 15minutes.

Preferentially, the application of the fixing composition takes placeafter the application of the dye composition, i.e. the compositioncomprising the ingredient i) as defined previously.

Between the dyeing step using the composition comprising the ingredienti) as defined previously and the fixing step, the keratin fibres arepreferentially rinsed with water.

When the ingredients i) and v) and optionally vii) as defined previouslyare not in the same composition, the pH of the composition that containsi) is preferentially inclusively between 4 and 10 and particularlybetween 5 and 7; and the pH of the composition that contains v) ispreferentially inclusively between 4 and 10 and particularly between 7and 10.

The dyeing and/or lightening process according to the invention may befollowed by shampooing with a standard shampoo and/or drying of thekeratin fibres.

According to particularly advantageous embodiments, the process isperformed in three different ways using compositions A, B and C inwhich:

-   -   the dye composition A contains:        -   i) at least one fluorescent disulfide dye in a concentration            inclusively between 0.01 g % and 5 g % and preferably            between 0.05 g % and 2 g %;        -   ii) at least one nonionic surfactant, preferably an APG, in            a concentration inclusively between 0.5 g % and 50 g % and            more particularly inclusively between 5 g % and 20 g %;        -   iii) at least one amphoteric surfactant in a concentration            of between 0.5 g % and 50 g % and preferably between 1 g %            and 20 g %;        -   vii) and optionally a polymeric organic thickener, which is            preferably cellulose-based, in a concentration inclusively            between 0.05 g % and 10 g % and more particularly            inclusively between 0.5 g % and 5 g %;        -   the pH of composition A preferably being inclusively between            4 and 10, and more particularly between 5 and 7;    -   the reducing composition B comprises:        -   v) at least one thiol reducing agent in a concentration            preferably inclusively between 0.5 g % and 50 g % and more            particularly inclusively between 10 g % and 30 g %;        -   iv) at least one alkaline agent preferably comprising an            amine group, in a concentration preferably inclusively            between 0.1 g % and 30 g % and more particularly between 0.5            g % and 5 g %;        -   and optionally at least one fragrance in a concentration            preferably inclusively between 0.01 g % and 10 g % and more            particularly between 0.2 g % and 2 g %;            the pH of composition B preferably being inclusively between            5 and 12, and more particularly inclusively between 7 and            10;    -   the fixing composition C comprises: vi) at least one oxidizing        agent in a concentration preferably inclusively between 0.01 g %        and 30 g % and more particularly between 0.5 g % and 5 g %, the        pH of composition C preferably being inclusively between 1.5 and        7 and more particularly between 2 and 5;    -    it being understood that the fixing composition may also        comprise a thickening organic polymer vii) as defined        previously; just like compositions A and/or B.

Variant 1:

The dye composition A is mixed with the reducing composition B in thefollowing proportions: 9 volumes of composition A are mixed with 1volume of composition B in a bowl. The mixture is applied to the hairwith a leave-on time preferably inclusively between 5 minutes and 1 hourand preferably between 10 minutes and 40 minutes. The hair is rinsed andis then optionally shampooed, shampooing preferably being performed, andthe hair is then dried.

Variant 2:

The dyeing formula A is mixed with the reducing composition B in thefollowing proportions: 9 volumes of composition A are mixed with 1volume of composition B in a bowl. The mixture is applied to the hairwith a leave-on time preferably inclusively between 5 minutes and 1 hourand more particularly inclusively between 10 minutes and 40 minutes.

The hair is optionally rinsed, preferably rinsed. The fixing compositionC is then applied to the hair with a leave-on time preferablyinclusively between 1 minute and 30 minutes and more particularlyinclusively between 3 minutes and 10 minutes.

The hair is rinsed and is then optionally shampooed, shampooingpreferably being performed, and the hair is then dried.

Variant 3:

The reducing formula is applied to the hair with a leave-on timepreferably inclusively between 5 minutes and 1 hour and moreparticularly inclusively between 10 minutes and 40 minutes. The hair isoptionally rinsed, preferably rinsed. The dye formula is applied to thehair with a leave-on time preferably inclusively between 5 minutes and 1hour and more particularly inclusively between 10 minutes and 40minutes. The hair is optionally rinsed, preferably rinsed. The fixingcomposition C is then applied to the hair with a leave-on timepreferably inclusively between 1 minute and 30 minutes and moreparticularly inclusively between 3 minutes and 10 minutes. The hair isrinsed and is then optionally shampooed, shampooing preferably beingperformed, and the hair is then dried.

3). Dyeing Kit of the Invention

A subject of the invention is also a multi-compartment dyeing device or“kit” comprising a first compartment containing a dye compositioncomprising the composition containing the ingredient i); a secondcompartment which contains a reducing agent v) as defined previously;the ingredients ii) to iv) and optionally vii) as defined previouslybeing divided among the first two compartments, and optionally a thirdcompartment comprising vi) at least one oxidizing agent as definedpreviously and optionally vii) as defined previously.

According to one variant, the device comprises a first compartmentcontaining a dye composition comprising the composition containing theingredients i) to iv) and optionally vii); a second compartment whichcontains at least one reducing agent v) as defined previously andoptionally a third compartment comprising at least one oxidizing agentvi) and optionally vii) as defined previously.

Alternatively, the dyeing device contains a first compartment containinga dye composition that comprises at least i) a protected-thiol dye, andthe ingredients ii) to iv) and optionally vii), a second compartmentcontaining an agent capable of deprotecting the protected thiol toliberate the thiol, a third compartment that contains at least onereducing agent v) as defined previously, and optionally a fourthcompartment comprising an oxidizing agent vi) and optionally vii) asdefined previously.

According to other variants:

-   -   the first compartment contains i) and ii) and optionally vii) as        defined previously and the second compartment comprises the        ingredients v), iv) and iii) as defined previously;    -   or alternatively the first compartment contains the ingredients        i), ii) and iii) and optionally vii) as defined previously and        the second compartment comprises the ingredients v) and iv);    -   or alternatively the first compartment contains the ingredients        i), iii) and iv) and optionally vii) as defined previously and        the second compartment comprises the ingredients v) and ii).

For these variants, a third compartment may be present, which containsan oxidizing agent vi) and optionally vii) as defined previously, andoptionally a fourth compartment containing an agent that is capable ofdeprotecting the protected thiol to liberate the thiol if the ingredienti) of the first compartment is a protected thiol.

Each of the devices mentioned above may be equipped with a means forapplying the desired mixture to the hair, for instance the devicesdescribed in patent FR 2 586 913.

The examples that follow serve to illustrate the invention without,however, being limiting in nature.

The direct thiol, protected-thiol or disulfide dyes of formula (I) thatare useful in the present invention are known compounds and may beprepared according to methods known to those skilled in the art,especially from the methods described in patent applications EP 1 647580, EP 2 004 759, WO 2007/110 541, WO 2007/110 540, WO 2007/110 539, WO2007/110 538, WO 2007/110 537, WO 2007/110 536, WO 2007/110 535, WO2007/110 534, WO 2007/110 533, WO 2007/110 532, WO 2007/110 531, EP 2070 988 and WO 2009/040 354.

Examples of Dyeing

Concentration of the Starting Materials in Unmodified Form

Composition A:

Ingredient Commercial name Supplier Amount Disulfide dye of formula 44having as 0.5 g %   counterion the disulfate ion SO₄ ²⁻ (ingredient i))Hydroxyethylcellulose (MW: 720 000) Natrosol 250 MR Aqualon 2 g %Mixture of methyl, butyl, ethyl, propyl and Sharomix 431 Clariant 0.12 g%   isobutyl p-hydroxybenzoates (7/57/22/14) (50/50 C₈/C₁₀)Alkylpolyglucoside (2) as Oramix CG 110 SEPPIC 10 g %  an aqueous 60%solution (ingredient ii)) Propylene glycol Propylene glycol Univar 4 g %USP/EP Polyethylene glycol (8 OE) Polyethylene glycol Stéarineries 6 g %400 DUB PEG 8 Dubois Sodium N-cocoylamidocarboxymethyl Miranol C2M Conc.Rhodia 6 g % glycinate as a 31.5% aqueous solution NP (ingredient iii))Water qs 100%

Commercial Ingredient name Supplier Amount Ammonium thioglycolate 71%Bruno  20 g % as a 71% aqueous Ammonium bock solution (pH 6)thioglycolate Diethylenetriaminepentaacetic Versenex 80 Univar 0.4 g %acid, pentasodium salt as a 40% aqueous solution Fragrance Fresh mintMane 0.8 g % Monoethanolamine Monoethanol- Univar 1.21 g %  amine CareOxyethylenated Oleyl Brij O20-SO-(MV) Croda   6 g % alcohol (20 OE)Water qs 100%

Ingredient Commercial name Supplier Amount Hydrogen peroxide as a 50%aqueous H₂O₂ Interox ST-50 Brenntag  0.48 g % solution (200 vol. aqueoushydrogen peroxide solution) Etidronic acid, tetrasodium salt, as aTurpinal 4 NL Brenntag  0.02 g % 30% aqueous solution Sodium salicylateSodium salicylate Merck 0.0035 g %  Tetrasodium pyrophosphateTetrasodium Penreac 0.004 g % decahydrate pyrophosphate decahydrate PRSPolydimethyldiallylammonium chloride at Merquat 100 Nalco 0.125 g % 40%in water Phosphoric acid Prayphos P5 85 Prayon 0.012 g % Crosslinkedethyltrimethylammonium Salcare SC 95 Ciba  1.3 g % methacrylate chloridehomopolymer as a 50% inverse emulsion in mineral oil Water qs 100%

9 parts of composition A are mixed with 1 part of composition B in abowl.

The mixture is applied to brown hair (dark hair having a tone height of4 (TH4)), with a leave-on time of 20 minutes.

The hair is rinsed.

The fixing formula C is applied to the hair, with a leave-on time of 5minutes.

The hair is rinsed, then shampooing is carried out and then the hair isdried.

Colorimetric Evaluation Results in the L*a*b* System for Evaluating theColoring of the Locks:

The color of the locks was evaluated in the L*a*b* system by means of aMINOLTA® CM 3600D spectrocolorimeter (Illuminant D65).

In this L*a*b* system, L* represents the lightness, a* indicates thegreen/red color axis and b* the blue/yellow color axis. The higher thevalue of L, the lighter or weaker the color. Conversely, the lower thevalue of L, the darker or much stronger the color. The higher the valueof a*, the redder the shade, and the higher the value of b*, the moreyellow the shade.

The variation in coloring between the TH4 dyed and treated locks of hairis measured by (ΔE) according to the following equation:ΔE=√{square root over ((L*−L _(o)*)²+(a*−a _(o)*)²+(b*−b_(o)*)²)}{square root over ((L*−L _(o)*)²+(a*−a _(o)*)²+(b*−b_(o)*)²)}{square root over ((L*−L _(o)*)²+(a*−a _(o)*)²+(b*−b _(o)*)²)}

In this equation, L*, a* and b* represent the values after treatment,and L₀*, a₀* and b₀* represent the values measured before treatment.

The greater the value of ΔE, the greater the difference in color betweenthe TH4 locks and the uncolored locks.

L* a* b* ΔE* TH4 reference 24.27 3.96 4.72 — After treatment A + B + C25.09 8.42 8.86 6.14

It is noted that the ΔE value is significantly high after treatment withcompositions A+B+C. A mahogany colouration is obtained which is intenseand persistent (even after several washing operations),

On the other hand the colour changed very little after the shampooingoperations, given the number of successive shampooing operations (evenafter more than 10 shampooing operations. It is also observed that thecoloration is particularly resistant vs. perspiration.

The invention claimed is:
 1. A cosmetic composition comprising: i) atleast one direct dye chosen from dyes of formula (I), comprising atleast one functional group chosen from disulfide, thiol, andprotected-thiol functional groups:A-(X)_(p)—C_(sat)—S—U  (I)  the salts thereof with an organic or mineralacid, optical or geometric isomers thereof, tautomers thereof, andsolvates thereof, wherein: U is a radical chosen from:a)—S—C′_(sat)—(X′)_(p′)-A′; and b)—Y; A and A′, which may be identicalor different, are chosen from polymethinyl radicals of formula (VI′)below:Ar—[C(R^(d))═C(R^(c))]_(m′)—W′⁺-(*)Q⁻  (VI′) wherein: W′⁺ is chosen fromdivalent heterocyclic and heteroaryl radicals chosen from cationicheterocyclic and heteroaryl groups ; Ar is an optionally substitutedaryl group; m′ is an integer ranging from 1 to 4 inclusive; R^(c) andR^(d), which may be identical or different, are chosen from hydrogen andoptionally substituted (C₁-C₈)alkyl groups, or alternatively R^(c)contiguous with W′⁺ and/or R^(d) contiguous with Ar form, together withthe atoms that bear them, a (hetero)cycloalkyl; Q⁻is an anioniccounterion; (*) represents the part of the chromophore linked to therest of the molecule of formula (I); Y is chosen from i) hydrogen; andii) thiol-function protecting groups; X and X′, which may be identicalor different, are chosen from linear or branched, saturated orunsaturated divalent C₁-C₃₀ hydrocarbon-based chains, optionallyinterrupted and/or optionally terminated at one or both of its ends withat least one divalent group chosen from: —N(R)—, —N⁺(R)(R)—, —O—, —S—,—CO—, and —SO₂— wherein R, which may be identical or different, ischosen from hydrogen and C₁-C₄ alkyl, hydroxyalkyl, and aminoalkylradicals; aromatic or non-aromatic, saturated or unsaturated, fused ornon-fused (hetero)cyclic radicals optionally comprising at least oneidentical or different, optionally substituted heteroatom; p and p′,which may be identical or different, are equal to 0 or 1; C_(sat) andC′_(sat), which may be identical or different, are chosen fromoptionally cyclic, optionally substituted linear or branched C₁-C₁₈alkylene chains; ii) at least one nonionic surfactant; iii) at least oneamphoteric surfactant; iv) at least one alkaline agent; and v) at leastone reducing agent chosen from thioglycolic acid, thiolactic acid,3-mercaptopropionic acid, thiomalic acid, 2,3-dimercaptosuccinic acid,cysteine, N-glycyl-L-cysteine, L-cysteinylglycine and also esters andsalts thereof, thioglycerol, cysteamine and C₁-C₄ acyl derivativesthereof, N-mesylcysteamine, N-acetylcysteine, N-mercaptoalkylamides ofsugars such as N-(mercapto-2-ethyl) gluconamide, pantetheine,N-(mercaptoalkyl)-ω-hydroxyalkylamides, N-mono- orN,N-dialkylmercapto-4-butyramides, aminomercaptoalkyl amides,N-(mercaptoalkyl)succinamic acids and N-(mercaptoalkyl)succinimides,alkylamino mercaptoalkyl amides, the azeotropic mixture of2-hydroxypropyl thioglycolate and of (2-hydroxy-1-methyl)ethylthioglycolate, mercaptoalkylamino amides, andN-mercaptoalkylalkanediamides.
 2. The composition according to claim 1,wherein the at least one direct dye of formula (I) is a disulfide dye,wherein U is a radical a) —S—C′_(sat)—(X′)_(p′)-A′.
 3. The compositionaccording to claim 2, wherein the at least one direct dye of formula (I)is a symmetrical disulfide dye of the following formula (Ia):A-(X)_(p)—C_(sat)—S—S—C′_(sat)—(X′)_(p′)-A′  (Ia) wherein A=A′, X=X′,p=p′, and C_(sat)=C′_(sat).
 4. The composition according to claim 1,wherein the at least one direct dye of formula (I) is a dye comprising athiol or protected-thiol function, wherein U is the radical b) Y, chosenfrom hydrogen and the following radicals: (C₁-C₄ )alkylcarbonyl; (C₁-C₄)alkylthiocarbonyl; (C₁-C₄ )alkoxycarbonyl; (C₁-C₄ )alkoxythiocarbonyl;(C₁-C₄ )alkylthio-thiocarbonyl; (di)(C₁-C₄ )(alkyl)aminocarbonyl;(di)(C₁-C₄ )(alkyl)aminothiocarbonyl; arylcarbonyl, for instancephenylcarbonyl; aryloxycarbonyl; aryl(C₁-C₄ )alkoxycarbonyl; (di)(C₁-C₄)(alkyl)aminocarbonyl; (C₁-C₄ )(alkyl)arylaminocarbonyl; carboxyl; SO₃⁻; M⁺ wherein M⁺ is chosen from alkali metal ions, or alternatively acounterion of the cationic chromophore A and M⁺ are absent; optionallysubstituted aryl; optionally substituted heteroaryl; optionallycationic, optionally substituted heterocycloalkyl;—C(NR′^(c)R′^(d))═N⁺R′^(e)R′^(f); An′″⁻ wherein R′^(c), R′^(d), R′^(e)and R′^(f), which may be identical or different, are chosen fromhydrogen atom and (C₁-C₄ )alkyl groups and An′″⁻ is a counterion;—C(NR′^(c)R′^(d))═NR═^(e); wherein R′^(C), R′^(d)and R′^(e) are definedabove; optionally substituted (di)aryl(C₁-C₄ )alkyl; optionallysubstituted (di)heteroaryl(C₁-C₄ )alkyl; CR¹R²R³ wherein R¹, R² and R³,which may be identical or different, are chosen from halogen and thefollowing groups: (C₁-C₄ )alkyl; (C₁-C₄ )alkoxy; optionally substitutedaryl; optionally substituted heteroaryl; P(Z¹)R′¹R′²R′³ wherein R′¹ andR′², which may be identical or different, are chosen from hydroxyl,(C₁-C₄ )alkoxy and alkyl groups, and Z¹ is chosen from oxygen andsulfur; sterically hindered rings; and optionally substitutedalkoxyalkyl.
 5. The composition according to claim 1, wherein, informula (I), C_(sat) and C′_(sat), which may be identical or different,are chosen from —(CH₂)_(k)—chains wherein k is an integer ranging from 1to 8 inclusive.
 6. The composition according to claim 1, wherein, informula (I), when p and p′ are equal to 1, X and X′, which may beidentical or different, are chosen from the following sequence:-(T)_(t)-(Z)_(z)-(T′)_(t′)- wherein the sequence is linked in formula(I) symmetrically as follows:—C_(sat)(or C′_(sat))-(T)_(t)-(Z)_(z)-(T′)_(t′)-(A or A′); wherein: Tand T′, which may be identical or different, are chosen from at leastone of: —O—; —S—; —N(R)—;  —N⁺(R)(R^(o))—; —S(O)_(2—; —S(O)) ₂—; and—C(O)—; wherein R, R^(o), which may be identical or different, arechosen from hydrogen, C₁-C₄ alkyl radicals, C₁-C₄ hydroxyalkyl radicalsand aryl(C₁-C₄ )alkyl radicals; and a cationic or non-cationic,optionally monocyclic heterocycloalkyl or heteroaryl radical, optionallycomprising two heteroatoms; t and t′, which may be identical ordifferent, are equal to 0 or 1; Z is chosen from: —(CH₂)_(m)— radicalswherein m is an integer ranging from 1 to 8 inclusive; —(CH₂CH₂O)_(q)—and —(OCH₂CH₂)_(q)— wherein q is an integer ranging from 1 to 5inclusive; aryl, alkylaryl and arylalkyl radicals wherein the alkylradical is chosen from C₁-C₄ alkyl radicals, optionally substituted withat least one group SO₃M wherein M is chosen from hydrogen, alkali metalions and ammonium groups substituted with at least one identical ordifferent, linear or branched C₁-C₁₈ alkyl radical optionally bearing atleast one hydroxyl group; z is 0 or
 1. 7. The composition according toclaim 1, wherein the at least one direct dye of formula (I) is adisulfide dyes chosen from those of formulae (XII) and thiol orprotected-thiol dyes chosen from those of formulae (XII′):

wherein: G and G′, which may be identical or different, are chosen from—NR_(c)R_(d), —NR′_(c)R′_(d) and C₁-C₆ alkoxy groups which areoptionally substituted; R_(c), R′_(c), R_(d) and R′_(d), which may beidentical or different, are chosen from hydrogen and optionallysubstituted aryl(C₁-C₄ )alkyl, C₁-C₆ alkoxy and C₁-C₆ alkyl groups; oralternatively two adjacent radicals R_(c) and R_(d), R′_(c) and R′_(d)borne by the same nitrogen atom, together form a heterocyclic orheteroaryl group; R_(g), R′_(g), R″_(g), R″′_(g), R_(h), R′_(h), R″_(h)and R″′_(h), which may be identical or different, are chosen fromhydrogen, halogen atoms, amino, C₁-C₄ alkylamino, C₁-C₄ dialkylamino,cyano, carboxyl, hydroxyl and trifluoromethyl groups, acylamino, C₁-C₄alkoxy, (poly)hydroxy(C₂-C₄ )alkoxy, alkylcarbonyloxy, alkoxycarbonyland alkylcarbonylamino radicals, acylamino, carbamoyl andalkylsulfonylamino radicals, aminosulfonyl radicals, and C₁-C₁₆ alkylradicals optionally substituted with a group chosen from C₁-C₁₂ alkoxy,hydroxyl, cyano, carboxyl, amino, C₁-C₄ alkylamino and C₁-C₄dialkylamino groups, or alternatively two alkyl radicals borne by thenitrogen atom of the amino group form a 5- to 7-membered heterocycleoptionally comprising another nitrogen or non-nitrogen heteroatom; oralternatively two groups R_(g) and R′_(g); R″_(g) and R″′_(g); R_(h),and R′_(h); R″_(h) and R′″_(h) borne by two adjacent carbon atomstogether form a benzo or indeno ring, a fused heterocycloalkyl or fusedheteroaryl group; wherein the benzo, indeno, heterocycloalkyl andheteroaryl rings are optionally substituted with an entity chosen fromhalogen atoms, amino, C₁-C₄ alkylamino, C₁-C₄ dialkylamino, nitro,cyano, carboxyl, hydroxyl and trifluoromethyl groups, acylamino, C₁-C₄alkoxy, (poly)hydroxy(C₂-C₄ )alkoxy, alkylcarbonyloxy, alkoxycarbonyland alkylcarbonylamino radicals, acylamino, carbamoyl andalkylsulfonylamino radicals, aminosulfonyl radicals, and C₁-C₁₆ alkylradicals optionally substituted with a group chosen from C₁-C₁₂ alkoxy,hydroxyl, cyano, carboxyl, amino, C₁-C₄ alkylamino, and C₁-C₄dialkylamino groups, or alternatively two alkyl radicals borne by thenitrogen atom of the amino group form a 5- to 7-membered heterocycleoptionally comprising another nitrogen or non-nitrogen heteroatom; oralternatively two groups R_(i) and R_(g); R″′_(i) and R″′_(g); R′_(i)and R′_(h); and/or R″_(i) and R″_(h) together form a fused(hetero)cycloalkyl; or alternatively when G is —NR_(c)R_(d) and G′ is—NR′_(c)R′_(d), two groups R_(c) and R′_(g); R′, and R″_(g); R_(d) andR_(g); R′_(d) and R″′_(g) together form a saturated heteroaryl orheterocycle, optionally substituted with at least one C₁-C₆ alkyl group,and optionally comprising at least one heteroatom chosen from nitrogenand oxygen; R_(i), R′_(i), R″_(i), and R″′_(i), which may be identicalor different, are chosen from hydrogen and C₁-C₄ alkyl groups; R₁, R₂,R₃, R₄, R′₁, R′₂, R′₃ and R′₄, which may be identical or different, arechosen from hydrogen and C₁-C₄ alkyl, C₁-C₁₂ alkoxy, hydroxyl, cyano,carboxyl, amino, C₁-C₄ alkylamino and C₁-C₄ dialkylamino groups, whereinthe alkyl radicals optionally form, together with the nitrogen atom thatbears them, a 5- to 7-membered heterocycle optionally comprising anothernitrogen or non-nitrogen heteroatom; T_(a) and T_(b), which may beidentical or different, are chosen from i) a covalent δbond, ii) atleast one radical chosen from —SO₂—, —O—, —S—, —N(R)—,—N⁺(R)(R^(o))—,and —CO—, wherein R and R^(o), which may be identical or different, arechosen from hydrogen and C₁-C₄ alkyl and C₁-C₄ hydroxyalkyl radicals;and aryl(C₁-C₄)alkyl radicals, and iii) cationic or non-cationic,heterocycloalkyl and heteroaryl radicals;

 which may be identical or different, are chosen from optionallysubstituted heterocyclic groups;

 is chosen from aryl and heteroaryl groups fused to the imidazolium orphenyl ring; or alternatively is absent from the imidazolium or phenylring; m, m′, n and n′, which may be identical or different, are integersranging from 0 to 6 inclusive, wherein the sums m+n and m′+n′, which maybe identical or different, are equal to integers ranging from 1 to 10inclusive; Y is chosen from hydrogen and the following protectinggroups: (C₁-C₄)alkylcarbonyl; arylcarbonyl; (C₁-C₄)alkoxycarbonyl;aryloxycarbonyl; aryl(C₁-C₄)alkoxycarbonyl;(di)(C₁-C₄)(alkyl)aminocarbonyl; (C₁-C₄)(alkyl)arylaminocarbonyl;optionally substituted aryl; 5- or 6-membered monocyclic heteroaryl; 5-or 6-membered cationic monocyclic heteroaryl; 8- to 11-membered cationicbicyclic heteroaryl; cationic heterocycles having the following formula:

—C(NH₂)═N⁺H₂An′″⁻; wherein An″′⁻ is an anionic counterion; —C(NH₂)═NH;SO₃ ⁻, M⁺ wherein M⁺ is a metal ion; and M′ is an anionic counterion. 8.The composition according to claim 1, wherein the at least one directdye of formula (I) is chosen from: dyes of formulae (XV) and (XV′)below:

 wherein in formulae (XV) and (XV′): R and R″′, which may be identicalor different, are chosen from hydroxyl, amino (NR_(a)R_(b)) and ammonium(N⁺R_(a)R_(b)R_(c))An⁻ groups; wherein R_(a), R_(b) and R_(c), which maybe identical or different, are chosen from hydrogen atom and(C₁-C₄)alkyl groups, and An⁻ is an anionic counterion;  or alternativelytwo alkyl groups R_(a) and R_(b) of the amino or ammonium group form a5- to 7-membered heterocycle optionally comprising another nitrogen ornon-nitrogen heteroatom; R′ and R″, which may be identical or different,are chosen from hydrogen and hydroxyl, amino (NR_(a)R_(b)) and ammonium(N⁺R_(a)R_(b)R_(c)) An⁻ groups; R_(g), R′_(g), R″_(g), R″′_(g), R_(h),R′_(h), R″_(h) and R″′_(h), which may be identical or different, arechosen from hydrogen, halogen atoms, amino, (di)(C₁-C₄)alkylamino,cyano, carboxyl, hydroxyl, trifluoromethyl, acylamino, C₁-C₄ alkoxy,(poly)hydroxy(C₂-C₄)alkoxy, (C₁-C₄)alkylcarbonyloxy,(C₁-C₄)alkoxycarbonyl, (C_(i)-C₄)alkylcarbonylamino, acylamino,carbamoyl and (C₁-C₄)alkylsulfonylamino groups, aminosulfonyl radicalsand (C₁-C₁₆)alkyl radicals optionally substituted with a group chosenfrom (C₁-C₁₂)alkoxy, hydroxyl, cyano, carboxyl, amino and(di)(C₁-C₄)alkylamino, or alternatively the two alkyl radicals borne bythe nitrogen atom of the amino group form a 5- to 7-membered heterocycleoptionally comprising another nitrogen or non-nitrogen heteroatom;R′_(i), R″_(i), R′″_(i); and R″″_(i), which may be identical ordifferent, are chosen from hydrogen and (C₁-C₄)alkyl groups; m and m′,which may be identical or different, are integers ranging from 1 to 10inclusive; p, p′, q and q′, which may be identical or different, areintegers ranging from 1 to 6 inclusive; M′ is an anionic counterion; andY is chosen from hydrogen and the following protective groups:(C₁-C₄)alkylcarbonyl; arylcarbonyl; (C₁-C₄)alkoxycarbonyl;aryloxycarbonyl; aryl(C₁-C₄)alkoxycarbonyl;(di)(C₁-C₄)(alkyl)aminocarbonyl; (C₁-C₄)(alkyl)arylaminocarbonyl;optionally substituted aryl; 5- or 6-membered monocyclic heteroaryl; 5-or 6-membered cationic monocyclic heteroaryl; 8- to 11-membered cationicbicyclic heteroaryl; cationic heterocycles of following formula:

—C(NH₂)═N⁺H₂ An′″⁻; wherein An″′⁻ is an anionic counterion; —C(NH₂)═NH;and SO₃ ⁻M⁺, wherein M⁺ is a metal ion; it being understood that whenthe compound of formula (XV) or (XV′) contains other cationic parts, itis combined with one or more anionic counterions that afford formula(XV) or (XV′) electrical neutrality; and dyes of formula (XVI) and(XVI′) below:

wherein in formula (XVI) and (XVI′): R₁ is chosen from C₁-C₆ alkylgroups substituted with at least one group chosen from hydroxyl groupsand —C(O)OR′ groups, wherein R′ is chosen from hydrogen and C₁-C₄ alkylgroups or alternatively a group —C(O)—O⁻ and, in the latter case, theanionic counterion An⁻ is absent; R₂ is chosen from C₁-C₆ alkyl groupsoptionally substituted with at least one hydroxyl group; oralternatively the groups R₁ and R₂ form, together with the nitrogen atomthat bears them, a saturated heterocyclic radical substituted with atleast one hydroxyl, (poly)hydroxy(C₁-C₄)alkyl and/or —C(O)OR′ groupwherein R′ is chosen from hydrogen and C₁-C₄ alkyl groups or a group—C(O)—O⁻ and, in the latter case, the anionic counterion An⁻ is absent;R₃ is chosen from hydrogen and —C(O)OR″ groups wherein R″ is chosen fromhydrogen, alkali metals and C₁-C₆ alkyl groups, or alternatively R₃ is agroup —C(O)—O⁻ and, in the latter case, the anionic counterion An⁻ isabsent; Z is chosen from divalent amido groups —C(O)—N(R)—, —N(R)—C(O)—,and divalent C₁-C₁₀ alkylene groups interrupted with an amido groupchosen from -(CH₂)_(n′)—C(O)—N(R)—(CH₂)_(p)—,—(CH₂)_(n″)—N(R)—C(O)-(CH₂)_(p)—, wherein n′ is an integer ranging from0 to 3 inclusive; p is an integer ranging from 0 to 4 inclusive, n″ isan integer ranging from 0 to 3 inclusive and R is chosen from hydrogenand C₁-C₆ alkyl groups; An⁻ is an anionic counterion; Y is chosen fromhydrogen and the following protective groups: (C₁-C₄)alkylcarbonyl;arylcarbonyl; (C₁-C₄)alkoxycarbonyl; aryloxycarbonyl;aryl(C₁-C₄)alkoxycarbonyl; (di)(C₁-C₄)(alkyl)aminocarbonyl;(C₁-C₄)(alkyl)arylaminocarbonyl; optionally substituted aryl; 5- or6-membered monocyclic heteroaryl; 5- or 6-membered cationic monocyclicheteroaryl; 8- to 11-membered cationic bicyclic heteroaryl; cationicheterocycles of following formula:

-C(NH₂)═N⁺H₂ An′″⁻; wherein An″′⁻ is an anionic counterion; —C(NH₂)═NH;and SO₃ ⁻M⁺, wherein M⁺ is a metal ion; it being understood that whenthe compound of formula (XVI) or (XVI′) contains other cationic parts,it is combined with one or more anionic counterions that afford formula(XVI) or (XVI′) electrical neutrality.
 9. The composition according toclaim 1, wherein the at least one direct dye of formula (I) is chosenfrom dyes of the following chemical structures:

wherein An⁻ and M′, which may be identical or different, are anioniccounterions.
 10. The composition according to claim 9, wherein An⁻ andM′ are identical and/or are chosen from halides and alkyl sulphates. 11.The composition according to Claim 9, wherein the at least one directdye of formula (I) is chosen from dyes of formulae 44 and
 55. 12. Thecomposition according to claim 1, wherein the at least one nonionicsurfactant ii) is chosen from: polyethoxylated, polypropoxylated and/orpolyglycerolated fatty alcohols, α-diols, and alkylphenols comprising afatty chain; copolymers of ethylene oxide and propylene oxide,condensates of ethylene oxide and propylene oxide on fatty alcohols;polyethoxylated fatty amides comprising from 2 to 30 mol of ethyleneoxide; polyglycerolated fatty amides comprising on average 1 to 5glycerol groups; oxyethylenated fatty acid esters of sorbitan comprisingfrom 2 to 30 mol of ethylene oxide; fatty acid esters of sucrose; fattyacid esters of polyethylene glycol; alkylpolyglycosides;N-alkylglucamine derivatives, amine oxides such as (C₁₀-C₁₄)alkylamineoxides and N-acylaminopropylmorpholine oxides.
 13. The compositionaccording to claim 12, wherein the at least one nonionic surfactant ii)is chosen from polyethoxylated, polypropoxylated and/or polyglycerolatedfatty alcohols, a-diols, and alkylphenols comprising a C₈-C₂₂ fattychain, wherein the number of ethylene oxide and/or propylene oxide unitsranges from 2 to 50 inclusive and/or the number of glycerol groupsranges from 2 to 30 inclusive.
 14. The composition according to claim12, wherein the at least one nonionic surfactant is chosen from(poly)ethoxylated fatty alcohols; glycerolated fatty alcohols; andalkylpolyglycosides.
 15. The composition according to claim 1, whereinthe at least one amphoteric surfactant iii) is chosen from (C₈-C₂₀alkyl)betaines, (C₈ ⁻C₂₀ alkyl)amido(C₂-C₈ alkyl)betaines and compoundsof formulae (XVIII) and (XIX) below:R_(a)—C(O)—NH—CH₂—CH₂—N⁺(R_(b))(R_(c))—CH₂—C(O)—O⁻  (XVIII) wherein informula (XVIII): R_(a) is chosen from C₁₀-C₃₀ alkyl and alkenyl groupsderived from an acid R_(a)—C(O)—OH, or a heptyl, nonyl or undecyl group;R_(b) is a p-hydroxyethyl group; and R_(c) is a carboxymethyl group; andR_(a′)—C(O)—NH—CH₂—CH₂—N(B)B′  (XIX) wherein in formula (XIX): B is—CH₂CH₂OX′; B′ is —(CH₂)_(z)—Y′, wherein z =1 or 2; X′ is chosen from—CH₂—C(O)—OH, —CH₂—C(O)—OZ′, —CH₂CH₂—C(O)—OH, —CH₂—CH₂—C(O)—OZ′, andhydrogen; Y′ is chosen from —C(O)—OH, —C(O)—OZ′, —CH₂—CH(OH)—SO₃H and—CH₂—CH(OH)—SO₃Z′; Z′ is chosen from ions derived from alkali oralkaline-earth metals; ammonium ions; and ions derived from an organicamine; R_(a′) is chosen from C₁₀-C₃₀ alkyl and alkenyl groups of an acidR_(a′)C(O)—OH, alkyl groups, and unsaturated C₁₇ groups and mixturesthereof.
 16. The composition according to claim 15, wherein the at leastone amphoteric surfactant iii) is chosen from cocoylamidopropylbetaineand cocoylbetaine and the N-cocoylamidocarboxymethyl glycinate of analkali metal.
 17. The composition according to claim 1, wherein the atleast one alkaline agent iv) is chosen from aqueous ammonia, alkalimetal carbonates and bicarbonates, sodium hydroxide, potassiumhydroxide, and mixtures thereof, alkanolamines, oxyethylenated and/oroxypropylenated ethylenediamines, amino acids and compounds of formula(XX) below:

wherein: W is chosen from divalent C₁-C₆ alkylene radicals optionallysubstituted with at least one radical chosen from hydroxyl and C₁-C₆alkyl radicals, and/or optionally interrupted with at least oneheteroatom chosen from oxygen and NR^(u); R^(x), R^(y), R^(z) R^(t) andR^(u), which may be identical or different, are chosen from hydrogen andC₁-C₆ alkyl, C₁-C₆ hydroxyalkyl and C₁-C₆ aminoalkyl radicals; andmixtures thereof.
 18. The composition according to claim 17, wherein theat least one alkaline agent iv) is ethanonlamine.
 19. The compositionaccording to claim 1, wherein the at least one reducing agent v) ischosen from thioglycolic acid, cysteine, and salts thereof.
 20. A methodfor dyeing and/or lightening keratin fibers, comprising applying to thekeratin fibers: i) at least one direct dye of formula (I) according toclaim 1; ii) at least one nonionic surfactant; iii) at least oneamphoteric surfactant; iv) at least one alkaline agent; and v) at leastone reducing agent chosen from thioglycolic acid, thiolactic acid,3-mercaptopropionic acid, thiomalic acid, 2,3-dimercaptosuccinic acid,cysteine, N-glycyl-L-cysteine, L-cysteinylglycine and also esters andsalts thereof, thioglycerol, cysteamine and C₁-C₄ acyl derivativesthereof, N-mesylcysteamine, N-acetylcysteine, N-mercaptoalkylamides ofsugars such as N-(mercapto-2-ethyl) gluconamide, pantetheine,N-(mercaptoalkyl)-ω-hydroxyalkylamides, N-mono- orN,N-dialkylmercapto-4-butyramides, aminomercaptoalkyl amides,N-(mercaptoalkyl)succinamic acids and N-(mercaptoalkyl) succinimides,alkylamino mercaptoalkyl amides, the azeotropic mixture of2-hydroxypropyl thioglycolate and of (2-hydroxy-1-methyl)ethylthioglycolate, mercaptoalkylamino amides, andN-mercaptoalkylalkanediamides; and vi) optionally at least one chemicaloxidizing agent; and vii) optionally at least one thickening organicpolymer; wherein the ingredients i) to vii) are applied to the keratinfibers together or separately.
 21. The method according to claim 20,comprising applying to the keratin fibers a reducing compositioncomprising iv) at least one alkaline agent and v) at least one reducingagent, followed by the application of a dye composition comprising i) atleast one direct dye of formula (I), ii), at least one nonionicsurfactant, iii) at least one amphoteric surfactant, and optionally vii)at least one thickening organic polymer.
 22. The method according toclaim 20, wherein the keratin fibers are dark keratin fibers having atone depth of less than or equal to 6, wherein the at least one directdye of formula (I) is chosen from: dyes of formulae (XII) and (XII′):

wherein: G and G′, which may be identical or different, are chosen from—NR_(c)R_(d), —NR′_(c)R′_(d) and C₁-C₆ alkoxy groups which areoptionally substituted; R_(g), R′_(g), R″_(g), R″′_(g), R_(h), R′_(h),R″_(h) and R″′_(h), which may be identical or different, are chosen fromhydrogen, halogen atoms, amino, C₁-C₄ alkylamino, C₁-C₄ dialkylamino,cyano, carboxyl, hydroxyl and trifluoromethyl groups, acylamino, C₁-C₄alkoxy, (poly)hydroxy(C₂-C₄)alkoxy, alkylcarbonyloxy, alkoxycarbonyl andalkylcarbonylamino radicals, acylamino, carbamoyl and alkylsulfonylaminoradicals, aminosulfonyl radicals, and C₁-C₁₆ alkyl radicals optionallysubstituted with a group chosen from C₁-C₁₂ alkoxy, hydroxyl, cyano,carboxyl, amino, C₁-C₄ alkylamino and C₁-C₄ dialkylamino groups, oralternatively two alkyl radicals borne by the nitrogen atom of the aminogroup form a 5- to 7-membered heterocycle optionally comprising anothernitrogen or non-nitrogen heteroatom; or alternatively two groups R_(g)and R′_(g); R″_(g) and R″′_(g); R_(h), and R′_(h); R″_(h) and R″′_(h)borne by two adjacent carbon atoms together form a benzo or indeno ring,a fused heterocycloalkyl or fused heteroaryl group; wherein the benzo,indeno, heterocycloalkyl and heteroaryl rings are optionally substitutedwith an entity chosen from halogen atoms, amino, C₁-C₄ alkylamino, C₁-C₄dialkylamino, nitro, cyano, carboxyl, hydroxyl and trifluoromethylgroups, acylamino, C₁-C₄ alkoxy, (poly)hydroxy(C₂-C₄)alkoxy, alkylcarbonyloxy, alkoxycarbonyl and alkylcarbonylamino radicals,acylamino, carbamoyl and alkylsulfonylamino radicals, aminosulfonylradicals, and C₁-C₁₆ alkyl radicals optionally substituted with a groupchosen from C₁-C₁₂ alkoxy, hydroxyl, cyano, carboxyl, amino, C₁-C₄alkylamino, and C₁-C₄ dialkylamino groups, or alternatively two alkylradicals borne by the nitrogen atom of the amino group form a 5- to7-membered heterocycle optionally comprising another nitrogen ornon-nitrogen heteroatom; or alternatively two groups R_(i); and R_(g);R″′_(i); and R″′_(g); R′_(i) and R′_(h); and/or R″_(i); and R″_(h)together form a fused (hetero)cycloalkyl; or alternatively when G is—NR_(c)R_(d) and G′ is —NR′_(c)R′_(d), two groups R_(c) and R′_(g);R′_(c) and R″_(g); R_(d) and R_(g); R′_(d) and R″′_(g) together form asaturated heteroaryl or heterocycle, optionally substituted with atleast one C₁-C₆ alkyl group, and optionally comprising at least oneheteroatom chosen from nitrogen and oxygen; R_(i), R′_(i), R″_(i), andR″′_(i), which may be identical or different, are chosen from hydrogenand C₁-C₄ alkyl groups; R₁, R₂, R₃, R₄, R′₁, R′₂, R′₃ and R′₄, which maybe identical or different, are chosen from hydrogen and C₁-C₄ alkyl,C₁-C₁₂ alkoxy, hydroxyl, cyano, carboxyl, amino, C₁-C₄ alkylamino andC₁-C₄ dialkylamino groups, wherein the alkyl radicals optionally form,together with the nitrogen atom that bears them, a 5- to 7-memberedheterocycle optionally comprising another nitrogen or non-nitrogenheteroatom; T_(a) and T_(b), which may be identical or different, arechosen from i) a covalent δbond, ii) at least one radical chosen from—SO₂—, —O—, —S—, —N(R)—, —N⁺(R)(R^(o))—, and —CO—, wherein R and R^(o),which may be identical or different, are chosen from hydrogen and C₁-C₄alkyl and C₁-C₄ hydroxyalkyl radicals; and aryl(C₁-C₄)alkyl radicals,and iii) cationic or non-cationic, heterocycloalkyl and heteroarylradicals;

 is chosen from aryl and heteroaryl groups fused to the imidazolium orphenyl ring; or alternatively is absent from the imidazolium or phenylring; m, m′, n and n′, which may be identical or different, are integersranging from 0 to 6 inclusive, wherein the sums m+n and m′+n′, which maybe identical or different, are equal to integers ranging from 1 to 10inclusive; Y is chosen from hydrogen and the following protectinggroups: (0₁-C₄)alkylcarbonyl; arylcarbonyl; (C₁-C₄)alkoxycarbonyl;aryloxycarbonyl; aryl(C₁-C₄)alkoxycarbonyl;(di)(C₁-C₄)(alkyl)aminocarbonyl; (C₁-C₄)(alkyl)arylaminocarbonyl;optionally substituted aryl; 5- or 6-membered monocyclic heteroaryl; 5-or 6-membered cationic monocyclic heteroaryl; 8- to 11-membered cationicbicyclic heteroaryl; cationic heterocycles having the following formula:

—C(NH₂)═N⁺H₂An′″⁻; wherein An′″⁻ is an anionic counterion; —C(NH₂)═NH;SO₃ ⁻, M⁺ wherein M⁺ is a metal ion; and M′ is an anionic counterion.23. The method according to claim 22, wherein the at least one directdye of formula (I) is chosen from dyes of the following chemicalstructures:


24. A multi-compartment dyeing device or kit for dyeing keratin fiberscomprising: a first compartment comprising a dye composition comprisingat least one direct dye of formula (I) according to claim 1; a secondcompartment comprising v) at least one reducing agent; and, optionally,a third compartment comprising vi) at least one chemical oxidizingagent; wherein the first and/or second compartment further comprises ii)at least one nonionic surfactant, iii) at least one amphotericsurfactant, iv) at least one alkaline agent, and/or vii) at least onethickening organic polymer.
 25. The method according to claim 21,wherein the keratin fibers have a tone height of less than or equal to6, wherein the at least one direct dye of formula (I) is chosen fromdyes of formulae (XV), (XV′):

wherein in formulae (XV) and (XV′): R and R″′, which may be identical ordifferent, are chosen from hydroxyl, amino (NR_(a)R_(b)) and ammonium(N⁺R_(a)R_(b)R_(c))An⁻ groups; wherein R_(a), R_(b) and R_(c), which maybe identical or different, are chosen from hydrogen atom and(C₁-C₄)alkyl groups, and An⁻ is an anionic counterion; or alternativelytwo alkyl groups R_(a) and R_(b) of the amino or ammonium group form a5- to 7-membered heterocycle optionally comprising another nitrogen ornon-nitrogen heteroatom; R′ and R″, which may be identical or different,are chosen from hydrogen and hydroxyl, amino (NR_(a)R_(b)) and ammonium(N⁺R_(a)R_(h)R_(c)) An⁻ groups; R_(g), R′_(g), R″_(g), R″′_(g), R_(h),R′_(h), R″_(h) and R″′_(h), which may be identical or different, arechosen from hydrogen, halogen atoms, amino, (di)(C₁-C₄)alkylamino,cyano, carboxyl, hydroxyl, trifluoromethyl, acylamino, C₁-C₄ alkoxy,(poly)hydroxy(C₂-C₄)alkoxy, (C₁-C₄)alkylcarbonyloxy,(C₁-C₄)alkoxycarbonyl, (C_(i)-C₄)alkylcarbonylamino, acylamino,carbamoyl and (C₁-C₄)alkylsulfonylamino groups, aminosulfonyl radicalsand (C₁-C₁₆)alkyl radicals optionally substituted with a group chosenfrom (C₁-C₁₂)alkoxy, hydroxyl, cyano, carboxyl, amino and(di)(C₁-C₄)alkylamino, or alternatively the two alkyl radicals borne bythe nitrogen atom of the amino group form a 5- to 7-membered heterocycleoptionally comprising another nitrogen or non-nitrogen heteroatom;R′_(i), R″_(i), R′″_(i); and R″″_(i), which may be identical ordifferent, are chosen from hydrogen and (C₁-C₄)alkyl groups; m and m′,which may be identical or different, are integers ranging from 1 to 10inclusive; p, p′, q and q′, which may be identical or different, areintegers ranging from 1 to 6 inclusive; M′ is an anionic counterion; andY is chosen from hydrogen and the following protective groups:(C₁-C₄)alkylcarbonyl; arylcarbonyl; (C₁-C₄)alkoxycarbonyl;aryloxycarbonyl; aryl(C₁-C₄)alkoxycarbonyl;(di)(C₁-C₄)(alkyl)aminocarbonyl; (C_(i)-C₄)(alkyl)arylaminocarbonyl;optionally substituted aryl; 5- or 6-membered monocyclic heteroaryl; 5-or 6-membered cationic monocyclic heteroaryl; 8- to 11-membered cationicbicyclic heteroaryl; cationic heterocycles of following formula:

—C(NH₂)═N⁺H₂ An⁻; wherein An⁻ is an anionic counterion; —C(NH₂)═NH; andSO₃ ⁻M⁺, wherein M⁺ is a metal ion; it being understood that when thecompound of formula (XV) or (XV′) contains other cationic parts, it iscombined with one or more anionic counterions that afford formula (XV)or (XV′) electrical neutrality.
 26. The method according to claim 21,wherein the keratin fibers have a tone height of less than or equal to6, wherein the at least one direct dye of formula (I) is chosen fromdyes of formulae (XVI), (XVI′):

wherein in formula (XVI) and (XVI′): R₁ is chosen from C₁-C₆ alkylgroups substituted with at least one group chosen from hydroxyl groupsand —C(O)OR′ groups, wherein R′ is chosen from hydrogen and C₁-C₄ alkylgroups or alternatively a group —C(O)—O⁻ and, in the latter case, theanionic counterion An⁻ is absent; R₂ is chosen from C₁-C₆ alkyl groupsoptionally substituted with at least one hydroxyl group; oralternatively the groups R₁ and R₂ form, together with the nitrogen atomthat bears them, a saturated heterocyclic radical substituted with atleast one hydroxyl, (poly)hydroxy(C₁-C₄)alkyl and/or —C(O)OR′ groupwherein R′ is chosen from hydrogen and C₁-C₄ alkyl groups or a group—C(O)—O⁻ and, in the latter case, the anionic counterion An⁻ is absent;R₃ is chosen from hydrogen and —C(O)OR″ groups wherein R″ is chosen fromhydrogen, alkali metals and C₁-C₆ alkyl groups, or alternatively R₃ is agroup —C(O)—O⁻ and, in the latter case, the anionic counterion An⁻ isabsent; Z is chosen from divalent amido groups —C(O)—N(R)—, —N(R)—C(O)—,and divalent C₁-C₁₀ alkylene groups interrupted with an amido groupchosen from —(CH₂)_(n′)—C(O)—N(R)—(CH₂)_(p)—,—(CH₂)_(n″)—N(R)—C(O)—(CH₂)_(p)—, wherein n′ is an integer ranging from0 to 3 inclusive; p is an integer ranging from 0 to 4 inclusive, n″ isan integer ranging from 0 to 3 inclusive and R is chosen from hydrogenand C₁-C₆ alkyl groups; An⁻ is an anionic counterion; Y is chosen fromhydrogen and the following protective groups: (C₁-C₄)alkylcarbonyl;arylcarbonyl; (C₁-C₄)alkoxycarbonyl; aryloxycarbonyl;aryl(C₁-C₄)alkoxycarbonyl; (di)(C₁-C₄)(alkyl)aminocarbonyl;(C₁-C₄)(alkyl)arylaminocarbonyl; optionally substituted aryl; 5- or6-membered monocyclic heteroaryl; 5- or 6-membered cationic monocyclicheteroaryl; 8- to 11-membered cationic bicyclic heteroaryl; cationicheterocycles of following formula:

—C(NH₂)═N⁺H₂ An′″⁻; wherein An⁻ is an anionic counterion; —C(NH₂)═NH;and SO₃ ⁻M⁺, wherein M⁺ is a metal ion; it being understood that whenthe compound of formula (XVI) or (XVI′) contains other cationic parts,it is combined with one or more anionic counterions that afford formula(XVI) or (XVI′) electrical neutrality.